Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalysts

ABSTRACT

Described are certain mono(cyclopentadienyl) Group IV B metal compounds, catalyst systems comprising such mono(cyclopentadienyl) metal compounds and an activator, and to a process using such catalyst systems for the production of polyolefins, particularly ethylene-α-olefin copolymers having a high molecular weight and high level of α-olefin incorporation.

This application is a continuation-in-part of U.S. Ser. No. 850,751,filed Mar. 13, 1992, now U.S. Pat. No. 5,264,405, which is acontinuation-in-part of U.S. Ser. No. 581,841, filed Sep. 19, 1990, nowU.S. Pat. No. 5,096,867, which is a continuation-in-part of U.S. Ser.No. 533,245 filed Jun. 4, 1990, now U.S. Pat. No. 5,055,438, which is acontinuation-in-part of U.S. Ser. No. 406,945 filed Sep. 13, 1989, nowabandoned. This application is also a continuation-in-part of U.S. Ser.No. 542,236 filed Jun. 22, 1990 and is a continuation-in-part of 938,198filed Aug. 28, 1992 now abandoned which is a continuation of U.S. Ser.No. 133,480, now abandoned, filed Dec. 22, 1987, which is acontinuation-in-part of U.S. Ser. No. 008,800, filed Jan. 30, 1987, nowabandoned and a continuation-in-part of U.S. Ser. No. 875,165 filed Apr.28, 1992, now U.S. Pat. No. 5,278,119, which is a continuation of U.S.Ser. No. 133,052, now abandoned, filed Dec. 21, 1987, which is acontinuation-in-part of U.S. Ser. No. 011,471, filed Jan. 30, 1987, nowabandoned.

FIELD OF THE INVENTION

This invention relates to certain monocyclopentadienyl metal compounds,to a catalyst system comprising a monocyclopentadienyl metal compoundand an activator, and to a process using such catalyst system for theproduction of polyolefins, particularly ethylene-α-olefin copolymershaving a high molecular weight and high level of α-olefin incorporation.

This invention relates to the discovery of various catalyst ligandstructure affects which are reflected in the activity of the catalystsystem and in the physical and chemical properties possessed by apolymer produced with a monocyclopentadienyl catalyst system.Accordingly, various species within the general class ofmonocyclopentadienyl metal catalysts have been discovered to be vastlysuperior in terms of the ability of such species to produceethylene-α-olefin copolymers of high molecular weight with high levelsof α-olefin comonomer incorporation and at high levels of catalystproductivity.

BACKGROUND OF THE INVENTION

As is well known, various processes and catalysts exist forhomopolymerization or copolymerization of olefins. For many applicationsit is of primary importance for a polyolefin to have a high weightaverage molecular weight while having a relatively narrow molecularweight distribution. A high weight average molecular weight, whenaccompanied by a narrow molecular weight distribution, provides apolyolefin or an ethylene-α-olefin copolymer with high strengthproperties.

Traditional Ziegler-Natta catalyst systems—a transition metal compoundcocatalyzed by an aluminum alkyl—are capable of producing polyolefinshaving a high molecular weight but a broad molecular weightdistribution.

More recently a catalyst system has been developed wherein thetransition metal compound has two or more cyclopentadienyl ringligands—such transition metal compound being referred to as ametallocene—which catalyzes the production of olefin monomers topolyolefins. Accordingly, metallocene compounds of a Group IV B metal,particularly, titanocenes and zirconocenes, have been utilized as thetransition metal component in such “metallocene” containing catalystsystems for the production of polyolefins and ethylene-α-olefincopolymers. When such metallocenes are cocatalyzed with an aluminumalkyl—as is the case with a traditional type Ziegler Natta catalystsystem—the catalytic activity of such metallocene catalyst system isgenerally too low to be of any commercial interest.

It has since become known that such metallocenes may be cocatalyzed withan alumoxane—rather than an aluminum alkyl—to provide a metallocenecatalyst system of high activity for the production of polyolefins.

The zirconium metallocene species, as cocatalyzed or activated with analumoxane, are commonly more active than their hafnium or titaniumanalogues for the polymerization of ethylene alone or together with anα-olefin comonomer. When employed in a non-supported form—i.e., as ahomogeneous or soluble catalyst system—to obtain a satisfactory rate ofproductivity even with the most active zirconocene species typicallyrequires the use of a quantity of alumoxane activator sufficient toprovide an aluminum atom to transition metal atom ratio (Al:TM) of atleast greater than 1000:1; often greater than 5000:1, and frequently onthe order of 10,000:1. Such quantities of alumoxane impart to a polymerproduced with such catalyst system an undesirable content of catalystmetal residue, i.e., an undesirable “ash” content (the nonvolatile metalcontent). In high pressure polymerization procedures using solublecatalyst systems wherein the reactor pressure exceeds about 500 bar onlythe zirconocene or hafnocene species may be used. Titanocene species aregenerally unstable at such high pressure unless deposited upon acatalyst support.

A wide variety of Group IV B transition metal compounds have been namedas possible candidates for an alumoxane cocatalyzed catalyst system.Although bis(cyclopentadienyl) Group IV B transition metal compoundshave been the most preferred and heavily investigated for use inalumoxane activated catalyst systems for polyolefin production,suggestions have appeared that mono and tris(cyclopentadienyl)transition metal compounds may also be useful. See, for example U.S.Pat. Nos. 4,522,982; 4,530,914 and 4,701,431. Suchmono(cyclopentadienyl) transition metal compounds as have heretoforebeen suggested as candidates for an alumoxane activated catalyst systemare mono(cyclopentadienyl) transition metal trihalides and trialkyls.

International Publication No. WO 87/03887 describes the use of acomposition comprising a transition metal coordinated to at least onecyclopentadienyl and at least one heteroatom ligand as a transitionmetal component for use in an alumoxane activated catalyst system forα-olefin polymerization. The composition is broadly defined as atransition metal, preferably of Group IV B of the Periodic Table, whichis coordinated with at least one cyclopentadienyl ligand and one tothree heteroatom ligands, the balance of the transition metalcoordination requirement being satisfied with cyclopentadienyl orhydrocarbyl ligands. Catalyst systems described by this reference areillustrated solely with reference to transition metal compounds whichare metallocenes, i.e., bis(cyclopentadienyl) Group IV B transitionmetal compounds.

At the Third Chemical Congress of North American held in Toronto, Canadain June 1988, John Bercaw reported upon efforts to use a compound of aGroup III B transition metal coordinated to a single cyclopentadienylheteroatom bridged ligand as a catalyst system for the polymerization ofolefins. Although some catalytic activity was observed under theconditions employed, the degree of activity and the properties observedin the resulting polymer product were discouraging of a belief that suchmono(cyclopentadienyl) transition metal compound could be usefullyemployed for commercial polymerization processes.

Although the metallocene/alumoxane catalyst system constituted animprovement relative to a traditional Ziegler-Natta catalyst system, aneed existed for discovering catalyst systems that permit the productionof higher molecular weight polyolefins and desirably with a narrowmolecular weight distribution. Further desired was a catalyst which,within reasonable ranges of ethylene to α-olefin monomer ratios, willcatalyze the incorporation of higher contents of α-olefin comonomers inthe production of ethylene-α-olefins copolymers.

EPO 416,815 discloses certain mono(cyclopentadienyl) metal compoundswhich are activated with an alumoxane cocatalyst. U.S. Pat. No.5,064,802 discloses certain mono(cyclopentadienyl) metal compounds whichare activated with a non-coordinating compatible anion of a Bronstedacid salt.

SUMMARY OF THE INVENTION

The present invention is a catalyst system including amono(cyclopentadienyl) metal compound and an activator component. Thecatalyst system is highly productive for polymerizing ethylene andα-olefins to produce a high molecular weight ethylene-α-olefin copolymerhaving a high content of α-olefin. More particularly, the presentinvention relates to certain mono(cyclopentadienyl) metal compoundswhich include an amido moiety having an aliphatic or alicyclichydrocarbyl group covalently bonded thereto through a primary orsecondary carbon atom.

DETAILED DESCRIPTION OF THE INVENTION

This invention comprises the discovery of a subgenus ofmono(cyclopentadienyl) metal compounds which, by reason of the presencetherein of ligands of a particular nature, provide a catalyst of greatlyimproved performance characteristics compared to known members of thegenus of mono(cyclopentadienyl) metal compounds. Themono(cyclopentadienyl) metal compounds of the present invention arerepresented by the formula:

wherein: M is Zr, Hf or Ti;

(C₅H_(4-x)R_(x)) is a cyclopentadienyl ring which is substituted withfrom zero to four substituent groups R, “x” is 0, 1 2, 3, or 4 denotingthe degree of substitution, and each substituent group g, is,independently, a radical selected from a group consisting of C₁-C₂₀hydrocarbyl radicals, substituted C₁-C₂₀ hydrocarbyl radicals whereinone or more hydrogen atoms is replaced by a halogen radical, an amidoradical, a phosphido radical, and alkoxy radical or any other radicalcontaining a Lewis acidic or basic functionality, C₁-C₂₀hydrocarbyl-substituted metalloid radicals wherein the metalloid isselected from the Group IV A of the Periodic Table of Elements, halogenradicals, amido radicals, phosphido radicals, alkoxy radicals,alkylborido radicals or any other radical containing Lewis acidic orbasic functionality; or (C₅H_(4-x)R_(x)) is a cyclopentadienyl ring inwhich at least two adjacent R-groups are joined forming a C₄-C₂₀ ring togive a saturated or unsaturated polycyclic cyclopentadienyl ligand suchas indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl;

R′ a radical selected from C₁-C₂₀ aliphatic and alicyclic hydrocarbylradicals wherein one or more hydrogen atoms may be replaced by radicalsselected from halogen, amido, phosphido, alkoxy or any other radicalcontaining a Lewis acidic or basic functionality, with the proviso thatR′ is covalently bonded to the nitrogen atom through a 1° or 2° carbonatom;

each Q is independently a halide, hydride, or substituted orunsubstituted C₁-C₂₀ hydrocarbyl, alkoxide, aryloxide, amide, phosphideor both Q together may be an alkylidene or a cyclometallated hydrocarbylor any other divalent anionic chelating ligand, with the proviso thatwhere any Q is a hydrocarbyl such Q is not a substituted orunsubstituted cyclopentadienyl radical,;

T is a covalent bridging group containing a Group IV A or V A elementsuch as, but not limited to, a dialkyl, alkylaryl or diaryl silicon orgermanium radical, alkyl or aryl phosphine or amine radical, or asubstituted or unsubstituted hydrocarbyl radical such as methylene,ethylene and the like which may be substituted with substituentsselected from alkyl and aryl radicals having from 1 to 20 carbon atoms;

L is a neutral Lewis base such as diethylether, tetraethylammoniumchloride, tetrahydrofuran, dimethylaniline, aniline, trimethylphosphine,n-butylamine, and the like; and

“w” is a number from 0 to 3.

L can also be a second transition metal compound of the same type suchthat the two metal centers M and M′ are bridged by Q and Q′, wherein M′has the same meaning as M and Q′ has the same meaning as Q. Such dimericcompounds are represented by the formula:

A preferred class of compounds of the present invention are representedby the formula:

wherein:

M represents Ti, Hf or Zr;

(C₅H_(4-x)N_(x)) is as defined above with respect to Formula I;

each of R¹ and R² are independently selected from C₁-C₂₀ hydrocarbylradicals;

each Q is independently selected from halide, hydride, substituted orunsubstituted C₁-C₂₀ hydrocarbyl radical, alkoxide, amide and phosphideradicals with the proviso that Q is not a substituted or unsubstitutedcyclopentadienyl radical;

R′ is selected from C₁-C₂₀ aliphatic and alicyclic hydrocarbyl radicalswith the proviso that R′ is covalently bonded to the nitrogen atomthrough a 1° or 2° carbon atom;

L_(w) is as defined above, and

x is an integer of from 0 to 4.

A more preferred class of compounds of the present invention are thosecompounds represented by Formula III wherein M is Ti; wherein R, R′, Q,and L_(w) are as defined above; and R¹ and R² are selected from alkyland aryl radicals having from 1 to 20 carbon atoms.

A most preferred class of compounds are represented by the above FormulaIII wherein R′ is selected from alicyclic radicals particularly thosehaving from 6 to 12 carbon atoms. Examples of specific compounds withinthe classes of compounds defined by Formula III include:

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclopropylamido)titaniumdimethyl;

dimethylsilyl(tetramethyleyclopentadienyl)-(cyclobutylamido)titaniumdimethyl;

dimethylsilyl(tetramethyleyclopentadienyl)-(cyclopentylamido)titaniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclohexylamido)titaniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cycloheptylamido)titaniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclooctylamido)titaniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclononylamido)titaniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclodecylamido)titaniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cycloundecylamido)titaniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclododecylamido)titaniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(sec-butylamido)titaniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(n-octylamido)titaniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(n-decylamido)titaniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(n-octadecylamido)titaniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclopropylamido)titaniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclobutylamido)titaniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclopentylamido)titaniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclohexylamido)titaniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cycloheptylamido)titaniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclooctylamido)titaniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclononylamido)titaniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclodecylamido)titanium,dimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cycloundecylamido)titaniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclododecylamido)titaniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(sec-butylamido)titaniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(n-octylamido)titaniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(n-decylamido)titaniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(n-octadecylamido)titaniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)(cyclopropylamido)titaniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclobutylamido)titaniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclopentylamido)titaniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclohexylamido)titaniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cycloheptylamido)titaniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclooctylamido)titaniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclononylamido)titaniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclodecylamido)titaniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cycloundecylamido)titaniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclododecylamido)titaniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(sec-butylamido)titaniumdimethyl;

diphenylsilyl(tetramethyleyclopentadienyl)-(n-octylamido)titaniumdimethyl;

diphenylsilyl(tetramethyleyclopentadienyl)-(n-decylamido)titaniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(n-octadecylamido)titaniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclopropylamido)titaniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclobutylamido)titaniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclopentylamido)titaniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclohexylamido)titaniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cycloheptylamido)titaniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclooctylamido)titaniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclononylamido)titaniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclodecylamido)titaniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cycloundecylamido)titaniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclododecylamido)titaniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(sec-butylamido)titaniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(n-octylamido)titaniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(n-decylamido)titaniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(n-octadecylamido)titaniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclopropylamido)titaniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclobutylamido)titaniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclopentylamido)titaniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclohexylamido)titaniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cycloheptylamido)titaniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclooctylamido)titaniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclononylamido)titaniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclodecylamido)titaniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cycloundecylamido)titaniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titaniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(sec-butylamido)titaniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(n-octylamido)titaniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(n-decylamido)titaniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(n-octadecylamido)titaniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclopropylamido)titaniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclobutylamido)titaniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclopentylamido)titaniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclohexylamido)titaniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cycloheptylamido)titaniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclooctylamido)titaniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclononylamido)titaniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclodecylamido)titaniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cycloundecylamido)titaniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclododecylamido)titaniumdiphenyl;

diphenylsilyl(tetramethyleyclopentadienyl)-(sec-butylamido)titaniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(n-octylamido)titaniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(n-decylamido)titaniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(n-octadecylamido)titaniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclopropylamido)hafniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclobutylamido)hafniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclopentylamido)hafniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclohexylamido)hafniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cycloheptylamido)hafniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclooctylamido)hafniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclononylamido)hafniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclodecylamido)hafniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cycloundecylamido)hafniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclododecylamido)hafniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(sec-butylamido)hafniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(n-octylamido)hafniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(n-decylamido)hafniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(n-octadecylamido)hafniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclopropylamido)hafniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclobutylamido)hafniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclopentylamido)hafniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclohexylamido)hafniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cycloheptylamido)hafniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclooctylamido)hafniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclononylamido)hafniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclodecylamido)hafniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cycloundecylamido)hafniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclododecylamido)hafniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(sec-butylamido)hafniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(n-octylamido)hafniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(n-decylamido)hafniumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(n-octadecylamido)hafniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclopropylamido)hafniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclobutylamido)hafniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclopentylamido)hafniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclohexylamido)hafniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cycloheptylamido)hafniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclooctylamido)hafniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclononylamido)hafniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclodecylamido)hafniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cycloundecylamido)hafniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclododecylamido)hafniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(sec-butylamido)hafniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(n-octylamido)hafniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(n-decylamido)hafniumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(n-octadecylamido)hafniumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclopropylamido)hafniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclobutylamido)hafniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclopentylamido)hafniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclohexylamido)hafniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cycloheptylamido)hafniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclooctylamido)hafniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclononylamido)hafniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclodecylamido)hafniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cycloundecylamido)hafniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclododecylamido)hafniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(sec-butylamido)hafniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(n-octylamido)hafniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(n-decylamido)hafniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(n-octadecylamido)hafniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclopropylamido)hafniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclobutylamido)hafniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclopentylamido)hafniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclohexylamido)hafniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cycloheptylamido)hafniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclooctylamido)hafniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclononylamido)hafniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclodecylamido)hafniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cycloundecylamido)hafniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclododecylamido)hafniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(sec-butylamido)hafniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(n-octylamido)hafniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(n-decylamido)hafniumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(n-octadecylamido)hafniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclopropylamido)hafniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclobutylamido)hafniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclopentylamido)hafniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclohexylamido)hafniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cycloheptylamido)hafniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclooctylamido)hafniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclononylamido)hafniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclodecylamido)hafniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cycloundecylamido)hafniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclododecylamido)hafniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(sec-butylamido)hafniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(n-octylamido)hafniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(n-decylamido)hafniumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(n-octadecylamido)hafniumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclopropylamido)zirconiumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclobutylamido)zirconiumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclopentylamido)zirconiumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclohexylamido)zirconiumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cycloheptylamido)zirconiumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclooctylamido)zirconiumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclononylamido)zirconiumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclodecylamido)zirconiumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cycloundecylamido)zirconiumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclododecylamido)zirconiumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(sec-butylamido)zirconiumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(n-octylamido)zirconiumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(n-decylamido)zirconiumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(n-octadecylamido)zirconiumdimethyl;

methylphenylsilyl(tetramethyleyclopentadienyl)-(cyclopropylamido)zirconiumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclobutylamido)zirconiumdimethyl;

methylphenylsilyl(tetramethyleyclopentadienyl)-(cyclopentylamido)zirconiumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclohexylamido)zirconiumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cycloheptylamido)zirconiumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclooctylamido)zirconiumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclononylamido)zirconiumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclodecylamido)zirconiumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cycloundecylamido)zirconiumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclododecylamido)zirconiumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(sec-butylamido)zirconiumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(n-octylamido)zirconiumdimethyl,

methylphenylsilyl(tetramethylcyclopentadienyl)-(n-decylamido)zirconiumdimethyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(n-octadecylamido)zirconiumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclopropylamido)zirconiumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclobutylamido)zirconiumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclopentylamido)zirconiumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclohexylamido)zirconiumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cycloheptylamido)zirconiumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclooctylamido)zirconiumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclononylamido)zirconiumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclodecylamido)zirconiumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cycloundecylamido)zirconiumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclododecylamido)zirconiumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(sec-butylamido)zirconiumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(n-octylamido)zirconiumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(n-decylamido)zirconiumdimethyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(n-octadecylyamido)zirconiumdimethyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclopropylamido)zirconiumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclobutylamido)zirconiumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclopentylamido)zirconiumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclohexylamido)zirconiumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cycloheptylamido)zirconiumdiphenyl;

dimethylsilyl(tetramethylcyclopentadientyl)-(cyclooctylamido)zirconiumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclononylamido)zirconiumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclodecylamido)zirconiumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cycloundecylamido)zirconiumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(cyclododecylamido)zirconiumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(sec-butylamido)zirconiumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(n-octylamido)zirconiumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(n-decylamido)zirconiumdiphenyl;

dimethylsilyl(tetramethylcyclopentadienyl)-(n-octadecylamido)zirconiumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclopropylamido)zirconiumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclobutylamido)zirconiumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclopentylamido)zirconiumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclohexylamido)zirconiumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cycloheptylamido)zirconiumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclooctylamido)zirconiumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclononylamido)zirconiumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclodecylamido)zirconiumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cycloundecylamido)zirconiumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclododecylamido)zirconiumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(sec-butylamido)zirconiumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(n-octylamido)zirconiumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(n-decylamido)zirconiumdiphenyl;

methylphenylsilyl(tetramethylcyclopentadienyl)-(n-octadecylamido)zirconiumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclopropylamido)zirconiumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclobutylamido)zirconiumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclopentylamido)zirconiumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclohexylamido)zirconiumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cycloheptylamido(zirconiumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclooctylamido)zirconiumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclononylamido)zirconiumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclodecylamido)zirconiumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cycloundecylamido)zirconiumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(cyclododecylamido)zirconiumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(sec-butylamido)zirconiumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(n-octylamido)zirconiumdiphenyl;

diphenylsilyl(tetramethylcyclopentadienyl)-(n-decylamido)zirconiumdiphenyl;

diphensylsilyl(tetramethylcyclopentadienyl)-(n-octadecylamido)zirconiumdiphenyl;

The above specific examples wherein each Q is methyl or each Q is phenylis prepared from the corresponding compound wherein each Q is chloro.The dichloro (both Q are Cl) species of each of the above compounds arealso within Formula II.

Another preferred class of compounds of the present invention are thosecompounds represented by the formula:

wherein R, R′, Q, M and L_(w) are as defined above; wherein T isselected from radicals of the formula (CR³R⁴) wherein R³ and R⁴ areindependently selected from hydrogen and C₁-C₂₀ hydrocarbyl radicals;and wherein y is 1 or 2.

A more preferred class of compounds are those compounds represented bythe above Formula IV wherein M is Ti. A most preferred class ofcompounds are those represented by the above Formula IV wherein M is Tiand wherein R³ and R⁴ are independently selected from hydrogen, C₁-C₆alkyl radicals and C₆-C₁₂ aryl radicals.

Examples of specific compounds within the class of compounds defined byFormula IV include:

methylene(tetramethylcyclopentadienyl)-(cyclopropylamido)titaniumdimethyl;

methylene(tetramethylcyclopentadienyl)-(cyclobutylamido)titaniumdimethyl;

methylene(tetramethylcyclopentadienyl)-(cyclopentylamido)titaniumdimethyl;

methylene(tetramethylcyclopentadienyl)-(cyclohexylamido)titaniumdimethyl;

methylene(tetramethylcyclopentadienyl)-(cycloheptylamido)titaniumdimethyl;

methylene(tetramethylcyclopentadienyl)-(cyclooctylamido)titaniumdimethyl;

methylene(tetramethylcyclopentadienyl)-(cyclononylamido)titaniumdimethyl;

methylene(tetramethylcyclopentadienyl)-(cyclodecylamido)titaniumdimethyl;

methylene(tetramethylcyclopentadienyl)-(cycloundecylamido)titaniumdimethyl;

methylene(tetramethylcyclopentadienyl)-(cyclododecylamido)titaniumdimethyl;

methylene(tetramethylcyclopentadienyl)-(sec-butylamido)titaniumdimethyl;

methylene(tetramethylcyclopentadienyl)-(n-octylamido)titanium dimethyl;

methylene(tetramethylcyclopentadienyl)-(n-decylamido)titanium dimethyl;

methylene(tetramethylcyclopentadienyl)-(n-octadecylamido)titaniumdimethyl;

dimethylmethylene(tetramethylcyclopentadienyl)-(cyclopropylamido)titaniumdimethyl;

dimethylmethylene(tetramethylcyclopentadienyl)-(cyclobutylamido)titaniumdimethyl;

dimethylmethylene(tetramethylcyclopentadienyl)-(cyclopentylamido)titaniumdimethyl;

dimethylmethylene(tetramethylcyclopentadienyl)-(cyclohexylamido)titaniumdimethyl;

dimethylmethylene(tetramethylcyclopentadienyl)-(cycloheptylamido)titaniumdimethyl;

dimethylmethylene(tetramethylcyclopentadienyl)-(cyclooctylamido)titaniumdimethyl;

dimethylmethylene(tetramethylcyclopentadienyl)-(cyclononylamido)titaniumdimethyl;

dimethylmethylene(tetramethylcyclopentadienyl)-(cyclodecylamido)titaniumdimethyl;

dimethylmethylene(tetramethylcyclopentadienyl)-(cycloundecylamido)titaniumdimethyl;

dimethylmethylene(tetramethylcyclopentadienyl)-(cyclododecylamido)titaniumdimethyl;

dimethylmethylene(tetramethylcyclopentadienyl)-(sec-butylamido)titaniumdimethyl;

dimethylmethylene(tetramethylcyclopentadienyl)-(n-octylamido)titaniumdimethyl;

dimethylmethylene(tetramethylcyclopentadienyl)-(n-decylamido)titaniumdimethyl;

dimethylmethylene(tetramethylcyclopentadienyl)-(n-octadecylamido)titaniumdimethyl;

diethylmethylene(tetramethylcyclopentadienyl)-(cyclopropylamido)titaniumdimethyl;

diethylmethylene(tetramethylcyclopentadienyl)-(cyclobutylamido)titaniumdimethyl;

diethylmethylene(tetramethylcyclopentadienyl)-(cyclopentylamido)titaniumdimethyl;

diethylmethylene(tetramethylcyclopentadienyl)-(cyclohexylamido)titaniumdimethyl;

diethylmethylene(tetramethylcyclopentadienyl)-(cycloheptylamido)titaniumdimethyl;

diethylmethylene(tetramethylcyclopentadienyl)-(cyclooctylamido)titaniumdimethyl;

diethylmethylene(tetramethylcyclopentadienyl)-(cyclononylamido)titaniumdimethyl;

diethylmethylene(tetramethylcyclopentadienyl)-(cyclodecylamido)titaniumdimethyl;

diethylmethylene(tetramethylcyclopentadienyl)-(cycloundecylamido)titaniumdimethyl;

diethylmethylene(tetramethylcyclopentadienyl)-(cyclododecylamido)titaniumdimethyl;

diethylmethylene(tetramethylcyclopentadienyl)-(sec-butylamido)titaniumdimethyl;

diethylmethylene(tetramethylcyclopentadienyl)-(n-octylamido)titaniumdimethyl;

diethylmethylene(tetramethylcyclopentadienyl)-(n-decylamido)titaniumdimethyl;

diethylmethylene(tetramethylcyclopentadienyl)-(n-octadecylamido)titaniumdimethyl;

ethylene(tetramethylcyclopentadienyl)-(cyclopropylamido)titaniumdimethyl;

ethylene(tetramethylcyclopentadienyl)-(cyclobutylamido)titaniumdimethyl;

ethylene(tetramethylcyclopentadienyl)-(cyclopentylamido)titaniumdimethyl;

ethylene(tetramethylcyclopentadienyl)-(cyclohexylamido)titaniumdimethyl;

ethylene(tetramethylcyclopentadienyl)-(cycloheptylamido)titaniumdimethyl;

ethylene(tetramethylcyclopentadienyl)-(cyclooctylamido)titaniumdimethyl;

ethylene(tetramethylcyclopentadienyl)-(cyclononylamido)titaniumdimethyl;

ethylene(tetramethylcyclopentadienyl)-(cyclodecylamido)titaniumdimethyl;

ethylene(tetramethylcyclopentadienyl)-(cycloundecylamido)titaniumdimethyl;

ethylene(tetramethylcyclopentadienyl)-(cyclododecylamido)titaniumdimethyl;

ethylene(tetramethylcyclopentadienyl)-(sec-butylamido)titanium dimethyl;

ethylene(tetramethycyclopentadienyl)-(n-octylamido)titanium dimethyl;

ethylene(tetramethylcyclopentadienyl)-(n-decylamido)titanium dimethyl;

ethylene(tetramethylcyclopentadienyl)-(n-octadecylamido)titaniumdimethyl;

1,1-dimethylethylene(tetramethylcyclopentadienyl)-(cyclopropylamido)titaniumdimethyl;

1,1-dimethylethylene(tetramethylcyclopentadienyl)-(cyclobutylamido)titaniumdimethyl;

1,1-dimethylethylene(tetramethylcyclopentadienyl)-(cyclopentylamido)titaniumdimethyl;

1,1-dimethylethylene(tetramethylcyclopentadienyl)-(cyclohexylamido)titaniumdimethyl;

1,1-dimethylethylene(tetramethylcyclopentadienyl)-(cycloheptylamido)titaniumdimethyl;

1,1-dimethylethylene(tetramethylcyclopentadienyl)-(cycloocytlamido)titaniumdimethyl;

1,1-dimethylethylene(tetramethylcyclopentadienyl)-(cyclononylamido)titaniumdimethyl;

1,1-dimethylethylene(tetramethylcyclopentadienyl)-(cyclodecylamido)titaniumdimethyl;

1,1-dimethylethylene(tetramethylcyclopentadienyl)-(cycloundecylamido)titaniumdimethyl;

1,1-dimethylethylene(tetramethylcyclopentadienyl)-(cyclododecylamido)titaniumdimethyl;

1,1-dimethylethylene(tetramethylcyclopentadienyl)-(sec-butylamido)titaniumdimethyl;

1,1-dimethylethylene(tetramethylcyclopentadienyl)-(n-octylamido)titaniumdimethyl;

1,1-dimethylethylene(tetramethylcyclopentadienyl)-(n-decylamido)titaniumdimethyl;

1,1-dimethylethylene(tetramethylcyclopentadienyl)-(n-octadecylamido)titaniumdimethyl;

1,1-dipropylethylene(tetramethylcyclopentadienyl)-(cyclopropylamido)titaniumdimethyl;

1,1-dipropylethylene(tetramethylcyclopentadienyl)-(cyclobutylamido)titaniumdimethyl;

1,1-dipropylethylene(tetramethylcyclopentadienyl)-(cyclopentylamido)titaniumdimethyl;

1,1-dipropylethylene(tetramethylcyclopentadienyl)-(cyclohexylamido)titaniumdimethyl;

1,1-dipropylethylene(tetramethylcyclopentadienyl)-(cycloheptylamido)titaniumdimethyl;

1,1-dipropylethylene(tetramethylcyclopentadienyl)-(cyclooctylamido)titaniumdimethyl;

1,1-dipropylethylene(tetramethylcyclopentadienyl)-(cyclononylamido)titaniumdimethyl;

1,1-dipropylethylene(tetramethylcyclopentadienyl)-(cyclodecylamido(titaniumdimethyl;

1,1-dipropylethylene(tetramethylcyclopentadienyl)-(cycloundecylamido)titaniumdimethyl;

1,1-dipropylethylene(tetramethylcyclopentadienyl)-(cyclododecylamido)titaniumdimethyl;

1,1-dipropylethylene(tetramethylcyclopentadienyl)-(sec-butylamido)titaniumdimethyl;

1,1-dipropylethylene(tetramethylcyclopentadienyl)-(n-octylamido)titaniumdimethyl;

1,1-dipropylethylene(tetramethylcyclopentadienyl)-(n-decylamido)titaniumdimethyl;

1,1-dipropylethylene(tetramethylcyclopentadienyl)-(n-octadecylamido)titaniumdimethyl;

1,2-dimethylethylene(tetramethylcyclopentadienyl)-(cyclopropylamido)titaniumdimethyl;

1,2-dimethylethylene(tetramethylcyclopentadienyl)-(cyclobutylamido)titaniumdimethyl;

1,2-dimethylethylene(tetramethylcyclopentadienyl)-(cyclopentylamido)titaniumdimethyl;

1,2-dimethylethylene(tetramethylcyclopentadienyl)-(cyclohexylamido)titaniumdimethyl;

1,2-dimethylethylene(tetramethylcyclopentadienyl)-(cycloheptylamido)titaniumdimethyl;

1,2-dimethylethylene(tetramethylcyclopentadienyl)-(cyclooctylamido)titaniumdimethyl;

1,2-dimethylethylene(tetramethylcyclopentadienyl)-(cyclononylamido)titaniumdimethyl;

1,2-dimethylethylene(tetramethylcyclopentadienyl)-(cyclodecylamido)titaniumdimethyl;

1,2-dimethylethylene(tetramethylcyclopentadienyl)-(cycloundecylamido)titaniumdimethyl;

1,2-dimethylethylene(tetramethylcyclopentadienyl)-(cyclododecylamido)titaniumdimethyl;

1,2-dimethylethylene(tetramethylcyclopentadienyl)-(sec-butylamido)titaniumdimethyl;

1,2-dimethylethylene(tetramethylcyclopentadienyl)-(n-octylamido)titaniumdimethyl;

1,2-dimethylethylene(tetramethylcyclopentadienyl)-(n-decylamido)titaniumdimethyl;

1,2-dimethylethylene(tetramethylcyclopentadienyl)-(n-octadecylamido)titaniumdimethyl;

1,2-dipropylethylene(tetramethylcyclopentadienyl)-(cyclpropylamido)titaniumdimethyl;

1,2-dipropylethylene(tetramethylcyclopentadienyl)-(cyclobutylamido)titaniumdimethyl;

1,2-dipropylethylene(tetramethylcyclopentadienyl)-(cyclopentylamido)titaniumdimethyl;

1,2-dipropylethylene(tetramethylcyclopentadienyl)-(cyclohexylamido)titaniumdimethyl;

1,2-dipropylethylene(tetramethylcyclopentadienyl)-(cycloheptylamido)titaniumdimethyl;

1,2-dipropylethylene(tetramethylcyclopentadienyl)-(cyclooctylamido)titaniumdimethyl;

1,2-dipropylethylene(tetramethylcyclopentadienyl)-(cyclononylamido)titaniumdimethyl;

1,2-dipropylethylene(tetramethylcyclopentadienyl)-(cyclodecylamido)titaniumdimethyl;

1,2-dipropylethylene(tetramethylcyclopentadienyl)-(cycloundecylamido)titaniumdimethyl;

1,2-dipropylethylene(tetramethylcyclopentadienyl)-(cyclododecylamido)titaniumdimethyl;

1,2-dipropylethylene(tetramethylcyclopentadienyl)-(sec-butylamido)titaniumdimethyl;

1,2-dipropylethylene(tetramethylcyclopentadienyl)-(n-octylamido)titaniumdimethyl;

1,2-dipropylethylene(tetramethylcyclopentadienyl)-(n-decylamido)titaniumdimethyl;

1,2-dipropylethylene(tetramethylcyclopentadienyl)-(n-octadecylamido)titaniumdimethyl;

2,2-dimethyethylene(tetramethylcyclopentadienyl)-(cyclopropylamido)titaniumdimethyl;

2,2-dimethyethylene(tetramethylcyclopentadienyl)-(cyclobutylamido(titaniumdimethyl;

2,2-dimethylethylene(tetramethylcyclopentadienyl)-(cyclopentylamido)titaniumdimethyl;

2,2-dimethylethylene(tetramethylcyclopentadienyl)-(cyclohexylamido)titaniumdimethyl;

2,2-dimethylethylene(tetramethylcyclopentadienyl)-(cycloheptylamido)titaniumdimethyl;

2,2-dimethylethylene(tetramethylcyclopentadienyl)-(cyclooctylamido)titaniumdimethyl;

2,2-dimethylethylene(tetramethylcyclopentadienyl)-(cyclononylamido)titaniumdimethyl;

2,2-dimethylethylene(tetramethylcyclopentadienyl)-(cyclodecylamido)titaniumdimethyl;

2,2-dimethylethylene(tetramethylcyclopentadienyl)-(cycloundecylamido)titaniumdimethyl;

2,2-dimethylethylene(tetramethylcyclopentadienyl)-(cyclododecylamido)titaniumdimethyl;

2,2-dimethylethylene(tetramethylcyclopentadienyl)-(sec-butylamido)titaniumdimethyl;

2,2-dimethylethylene(tetramethylcyclopentadienyl)-(n-octylamido)titaniumdimethyl;

2,2-dimethylethylene(tetramethylcyclopentadienyl)-(n-decylamido)titaniumdimethyl;

2,2-dimethylethylene(tetramethylcyclopentadienyl)-(n-octadecylamido)titaniumdimethyl;

2,2-dipropylethylene(tetramethylcyclopentadienyl)-(cyclopropylamido)titaniumdimethyl;

2,2-dipropylethylene(tetramethylcyclopentadienyl)-(cyclobutylamido)titaniumdimethyl;

2,2-dipropylethylene(tetramethylcyclopentadienyl)-(cyclopentylamido)titaniumdimethyl;

2,2-dipropylethylene(tetramethylcyclopentadienyl)-(cyclohexylamido)titaniumdimethyl;

2,2-dipropylethylene(tetramethylcyclopentadienyl)-(cycloheptylamido)titaniumdimethyl;

2,2-dipropylethylene(tetramethylcyclopentadienyl)-(cyclooctylamido)titaniumdimethyl;

2,2-dipropylethylene(tetramethylcyclopentadienyl)-(cyclononylamido)titaniumdimethyl;

2,2-dipropylethylene(tetramethylcyclopentadienyl)-(cyclodecylamido)titaniumdimethyl;

2,2-dipropylethylene(tetramethylcyclopentadienyl)-(cycloundecylamido)titaniumdimethyl;

2,2-dipropylethylene(tetramethylcyclopentadienyl)-(cyclododecylamido)titaniumdimethyl;

2,2-dipropylethylene(tetramethylcyclopentadienyl)-(sec-butylamido)titaniumdimethyl;

2,2-dipropylethylene(tetramethylcyclopentadienyl)-(n-octylamido)titaniumdimethyl;

2,2-dipropylethylene(tetramethylcyclopentadienyl)-(n-decylamido)titaniumdimethyl;

2,2-dipropylethylene(tetramethylcyclopentadienyl)-(n-octadecylamido)titaniumdimethyl;

1,1-diphenylethylene(tetramethylcyclopentadienyl)-(cyclopropylamido)titaniumdimethyl;

1,1-diphenylethylene(tetramethylcyclopentadienyl)-(cyclobutylamido)titaniumdimethyl;

1,1-diphenylethylene(tetramethylcyclopentadienyl)-(cyclopentylamido)titaniumdimethyl;

1,1-diphenylethylene(tetramethylcyclopentadienyl)-(cyclohexylamido)titaniumdimethyl;

1,1-diphenylethylene(tetramethylcyclopentadienyl)-(cycloheptylamido)titaniumdimethyl;

1,1-diphenylethylene(tetramethylcyclopentadienyl)-(cyclooctylamido)titaniumdimethyl;

1,1-diphenylethylene(tetramethylcyclopentadienyl)-(cyclononylamido)titaniumdimethyl;

1,1-diphenylethylene(tetramethylcyclopentadienyl)-(cyclodecylamido)titaniumdimethyl;

1,1-diphenylethylene(tetramethylcyclopentadienyl)-(cycloundecylamido)titaniumdimethyl;

1,1-diphenylethylene(tetramethylcyclopentadienyl)-(cyclododecylamido)titaniumdimethyl;

1,1-diphenylethylene(tetramethylcyclopentadienyl)-(sec-butylamido)titaniumdimethyl;

1,1-diphenylethylene(tetramethylcyclopentadienyl)-(n-octylamido)titaniumdimethyl;

1,1-diphenylethylene(tetramethylcyclopentadienyl)-(n-decylamido)titaniumdimethyl;

1,1-diphenylethylene(tetramethylcyclopentadienyl)-(n-octadecylamido)titaniumdimethyl;

1,2-diphenylethylene(tetramethylcyclopentadienyl)-(cyclopropylamido)titaniumdimethyl;

1,2-diphenylethylene(tetramethylcyclopentadienyl)-(cyclobutylamido)titaniumdimethyl;

1,2-diphenylethylene(tetramethylcyclopentadienyl)-(cyclopentylamido)titaniumdimethyl;

1,2-diphenylethylene(tetramethylcyclopentadienyl)-(cyclohexylamido)titaniumdimethyl;

1,2-diphenylethylene(tetramethylcyclopentadienyl)-(cycloheptylamido)titaniumdimethyl;

1,2-diphenylethylene(tetramethylcyclopentadienyl)-(cyclooctylamido)titaniumdimethyl;

1,2-diphenylethylene(tetramethylcyclopentadienyl)-(cyclononylamido)titaniumdimethyl;

1,2-diphenylethylene(tetramethylcyclopentadienyl)-(cyclodecylamido)titaniumdimethyl;

1,2-diphenylethylene(tetramethylcyclopentadienyl)-(cycloundecylamido)titaniumdimethyl;

1,2-diphenylethylene(tetramethylcyclopentadienyl)-(cyclododecylamido)titaniumdimethyl;

1,2-diphenylethylene(tetramethylcyclopentadienyl)-(sec-butylamido)titaniumdimethyl;

1,2-diphenylethylene(tetramethylcyclopentadienyl)-(n-octylamido)titaniumdimethyl;

1,2-diphenylethylene(tetramethylcyclopentadienyl)-(n-decylamido)titaniumdimethyl;

1,2-diphenylethylene(tetramethylcyclopentadienyl)-(n-octadecylamido)titaniumdimethyl;

2,2-diphenylethylene(tetramethylcyclopentadienyl)-(cyclopropylamido)titaniumdimethyl;

2,2-diphenylethylene(tetramethylcyclopentadienyl)-(cyclobutylamido)titaniumdimethyl;

2,2-diphenylethylene(tetramethylcyclopentadienyl)-(cyclopentylamido)titaniumdimethyl;

2,2-diphenylethylene(tetramethylcyclopentadienyl)-(cyclohexylamido)titaniumdimethyl;

2,2-diphenylethylene(tetramethylcyclopentadienyl)-(cycloheptylamido)titaniumdimethyl;

2,2-diphenylethylene(tetramethylcyclopentadienyl)-(cyclooctylamido)titaniumdimethyl;

2,2-diphenylethylene(tetramethylcyclopentadienyl)-(cyclononylamido)titaniumdimethyl;

2,2-diphenylethylene(tetramethylcyclopentadienyl)-(cyclodecylamido)titaniumdimethyl;

2,2-diphenylethylene(tetramethylcyclopentadienyl)-(cycloundecylamido)titaniumdimethyl;

2,2-diphenylethylene(tetramethylcyclopentadienyl)-(cyclododecylamido)titaniumdimethyl;

2,2-diphenylethylene(tetramethylcyclopentadienyl)-(sec-butylamido)titaniumdimethyl;

2,2-diphenylethylene(tetramethylcyclopentadienyl)-(n-octylamido)titaniumdimethyl;

2,2-diphenylethylene(tetramethylcyclopentadienyl)-(n-decylamido)titaniumdimethyl;

2,2-diphenylethylene(tetramethylcyclopentadienyl)-(n-octadecylamido)titaniumdimethyl;

The above named specific compounds wherein each Q is methyl are preparedfrom the corresponding compound wherein each Q is chloro. Thus, specificcompounds within Formula IV are those wherein each Q is chloro. Also,the corresponding compounds wherein each Q is phenyl, M is zirconium ofhafnium in place of titanium and (CR³R⁴)y is methylphenylmethylene,tetramethylethylene or tetraethylethylene are also specific compoundswithin the above Formula IV.

Herein a 1° carbon atom is one which is a methyl radical or a carbonatom which is bonded to only one other carbon atom; a 2° carbon atom isone which is bonded to only two other carbon atoms, and a 3° carbon atomis bonded to three other carbon atoms. Preferably the R′ alicyclic oraliphatic hydrocarbyl group has three or more carbon atoms and is bondedto the nitrogen atom through a 2° carbon atom; most preferably thehydrocarbyl group is alicyclic.

Mono(cyclopentadienyl) metal compounds of the present invention havebeen discovered to produce a highly productive catalyst system whichproduces an ethylene-α-olefin copolymer of significantly greatermolecular weight and α-olefin comonomer content as compared with otherspecies of mono(cyclopentadienyl) metal compounds when utilized in anotherwise identical catalyst system under identical polymerizationconditions. Further, within this subgenus of metal compounds it has beenfound that the nature and degree of substitution groups (R) of thecyclopentadienyl ring can be varied to produce a catalyst system havinga “catalyst reactivity ratio (r₁)” which may be varied from a high tolow value as may be most desired to best suit the catalyst system to aparticular type of polymerization process. Particularly it has beenfound that as the number of substituents (R), which are preferablyhydrocarbyl substituents increases, the reactivity ratio (r₁) decreases,the lowest reactivity ratios being obtained by a titanium compoundhaving a tetrahydrocarbyl substituted cyclopentadienyl group, preferablya tetramethylcyclopentadienyl group.

The most preferred class of cyclopentadienyl metal compounds arerepresented by the formula:

wherein Q, L, R′, R, “x” and “w” are as previously defined and R¹ and R²are each independently selected from C₁ to C₂₀ hydrocarbyl radicalswherein one or more hydrogen atoms is replaced by a halogen atom; R¹ andR² may also be joined forming a C₃ and C₂₀ ring which incorporates thesilicon bridge.

Among this class of compounds of Formula V, various substituent andligand affects have been discovered which significantly affect theproperties of a catalyst system. The nature and degree of substitutions(R) in the cyclopentadienyl ring was found to significantly influencethe catalyst ability to incorporate α-olefin comonomers when producingan ethylene-α-olefin copolymer. For the greatest amount of comonomerincoporation, the cyclopentadienyl ring should be fully substituted(x=4) with hydrocarbyl groups (R), most preferably methyl groups. Thisaffect is demonstrated by a comparison between Examples 83 to 85. Next,the nature of the R′ ligand of the amido group significantly influencesthe capability of a catalyst to incorporate α-olefin comonomer. Amidogroup R′ ligands which are aliphatic or alicyclic hydrocarbyl ligandsbonded to the nitrogen atom through a 1° or 2° carbon atom provide for agreater degree of α-olefin comonomer incorporation than do R′ groupsbonded through a 3° carbon atom or bearing aromatic carbon atoms.Further, wherein the R′ ligand is bonded to the nitrogen atom through a2° carbon atom, the activity of the catalyst is greater when the R′substituent is alicyclic than when R′ is bonded to the nitrogen througha 1° carbon atom of an aliphatic group of identical carbon number. Withregard to an alicyclic hydrocarbyl R′ ligand it has been found that asthe number of carbon atoms thereof increases the molecular weight of theethylene-α-olefin copolymer increases while the amount of α-olefincomonomer incorporated remains about the same or increases. Further, asthe carbon number of the alicyclic hydrocarbyl ligand increases theproductivity of the catalyst system increases. This is demonstrated byExamples 71-76. Accordingly, the R′ ligand most preferred iscyclododecyl (C₁₂H₂₃).

The effect of the bridging group ligands R¹ and R² has been found to beof less significance. The nature of the R¹ and R² ligands exerts a smalleffect upon the activity of a catalyst. For greatest catalyst actvitythe R¹ and R² ligands are preferably alkyl, most preferably methyl. TheQ anionic ligands of the transition metal have not been observed toexert any particular influence on the catalyst or polymer properties, asdemonstrated by comparison of Examples 71 and 86. Accordingly, as aconvenience in the production of the transitional metal component the Qligands are preferably chlorine or methyl.

The compounds most preferred for reasons of their high catalyst activityin combination with an ability to produce high molecular weightethylene-α-olefin copolymers of high comonomer content is represented bythe formula

wherein R¹ and R² are each independently a C₁ to C₃ hydrocarbyl radical,each Q is independently a halide or alkyl radical, R′ is an aliphatic oran alicyclic hydrocarbyl radical of the formula (C_(n)H_(2+b)) wherein“n” is a number from 3 to 20 and “b” is +1 in which case the ligand isaliphatic or −1 in which case the ligand is alicyclic. Of thesecompounds, the most preferred is that compound wherein R¹ and R² aremethyl, each Q is methyl, n is 12, and the hydrocarbyl radical isalicyclic (i.e., b is −1). Most preferred is that compound wherein theCnH₂n−1 hydrocarbyl radical is a cyclododecyl group. Hereafter thiscompound is referred to for convenience as Me₂Si(C₅Me₄) (NC₁₂H₂₃)TiQ₂.

All of the above-defined mono(cyclopentadienyl) metal compounds areuseful, in combination with an activator or cocatalyst, to polymerizeα-olefins. Suitable activators include alumoxanes and activatorscomprising a cation and a non-coordinating compatible anion.

The alumoxane component is an oligomeric compound which may berepresented by the general formula (R³—Al—O)_(m) which is a cycliccompound, or may be R⁴(R⁵—Al—O—)_(m)—AlR⁶ ₂ which is a linear compound.An alumoxane is generally a mixture of both the linear and cycliccompounds. In the general alumoxane formula R³, R⁴, R⁵ and R⁶ are,independently a C₁-₅ alkyl radical, for example, methyl, ethyl, propyl,butyl or pentyl and “m” is an integer from 1 to about 50. Mostpreferably, R³, R⁴, R⁵ and R⁶ are each methyl and “m” is at least 4.When an alkyl aluminum halide is employed in the preparation of thealumoxane, one or more R³⁻⁶ groups may be halide.

As is now well known, alumoxanes can be prepared by various procedures.For example, a trialkyl aluminum may be reacted with water, in the formof a moist inert organic solvent; or the trialkyl aluminum may becontacted with a hydrated salt, such as hydrated copper sulfatesuspended in an inert organic solvent, to yield an alumoxane. Generally,however prepared, the reaction of a trialkyl aluminum with a limitedamount of water yields a mixture of both linear and cyclic species ofalumoxane.

Suitable alumoxanes utilized in the catalyst systems of this inventionare those prepared by the hydrolysis of a trialkylaluminum; such astrimethylaluminum, triethylaluminum, tripropylaluminum;triisobutylaluminum, dimethylaluminumchloride,diisobutylaluminumchloride, diethylaluminumchloride, and the like. Themost preferred alumoxane for use is methylalumoxane (MAO).Methylalumoxanes having an average degree of oligomerization of fromabout 4 to about 25 (“m”=4 to 25), with a range of 13 to 25, are themost preferred.

Activators comprising a non-coordinating compatible anion component aredescribed in U.S. Pat. No. 5,198,401 which is incorporated herein byreference. Compounds useful as the activator compound, in thepreparation of the catalyst comprise a cation, preferably a Bronstedacid capable of donating a proton, and a compatible non-coordinatinganion containing a single coordination complex comprising acharge-bearing metal or metalloid core which is relatively large(bulky), capable of stabilizing the active catalyst species (the GroupIV-B cation) which is formed when the metallocene and activatorcompounds are combined, and said anion is sufficiently labile to bedisplaced by olefinic, diolefinic and acetylenically unsaturatedsubstrates or other neutral Lewis bases such as ethers, nitriles and thelike. It is well known that reactive cations other than Bronsted acidscapable of donating a proton are also useful. Examples of such othercations include ferrocenium triphenylcarbonium and triethylsilyliniumcations. Any metal or metalloid capable of forming a coordinationcomplex which is resistant to degradation by water (or other Bronsted orLewis Acids) may be used or contained in the anion of the secondactivator compound. Suitable metals include, but are not limited to,aluminum, gold, platinum and the like. Suitable metalloids include, butare not limited to, boron, phosphorus, silicon and the like.

Compounds containing anions which comprise coordination complexescontaining a single metal or metalloid atom are, of course, well knownand many, particularly compounds containing a single boron atom in theanion portion, are available commercially. In light of this, saltscontaining anions comprising a coordination complex containing a singleboron atom are preferred. In general, the second activator compoundsuseful in the preparation of the catalysts of this invention may berepresented by the following general formula:

[(L′-H)⁺]_(d)[(M′)^(m+)Q′″₁Q′″_(2 . . .) Q′″_(n)]^(d-)

wherein:

L′ is a neutral Lewis base;

H is a hydrogen atom;

[L′-H] is a Bronsted acid;

M′ is a metal or metalloid;

Q′″₁ to Q′″_(n) are, independently, hydride radicals, bridged orunbridged dialkylamido radicals, alkoxide and aryloxide radicals,hydrocarbyl and substituted hydrocarbyl radicals, halocarbyl andsubstituted halocarbyl radicals, and hydrocarbyl- andhalocarbyl-substituted organometalloid radicals and any one, but notmore than one, of Q₁ to Q_(n) may be a halide radical;

m is an integer representing the formal valence charge of M′;

n is the total number of ligands Q; and

d is an integer representing the total charge on the anion.

Activator compounds comprising boron which are particularly useful inthe preparation of catalysts of this invention are represented by thefollowing general formula:

[L′-H]⁺[BAr₁Ar₂X₃X₄]⁻

wherein:

L′ is a neutral Lewis base;

H is a hydrogen atom;

[L′-H]⁺ is a Bronsted acid;

B is boron in a valence state of 3⁺;

Ar₁ and Ar₂ are the same or different substituted-aromatic hydrocarbonradicals and may be linked to each other through a stable bridginggroup; and

X₃ and X₄ are, independently, hydride radicals, halide radicals, withthe proviso that only X₃ or X₄ will be halide, hydrocarbyl radicals,substituted-hydrocarbyl radicals, halocarbyl radicals,substituted-halocarbyl radicals, hydrocarbyl- and halocarbyl-substitutedorganometalloid radicals, dialkylamido radicals, and alkoxy and aryloxyradicals.

In general, Ar₁ and Ar₂ may, independently, be any aromatic orsubstituted-aromatic hydrocarbon radical. Suitable aromatic radicalsinclude, but are not limited to, phenyl, naphthyl and anthracenylradicals. Suitable substituents on useful substituted-aromatichydrocarbon radicals, include, but are not necessarily limited to,hydrocarbyl radicals, organometalloid radicals, alkoxy radicals,alkylamido radicals, fluoro and fluorohydrocarbyl radicals and the likesuch as those useful as X₃ or X₄. The substituent may be ortho, meta orpara, relative to the carbon atom bonded to the boron atom. When eitheror both X₃ and X₄ are a hydrocarbyl radical, each may be the same or adifferent aromatic or substituted-aromatic radical as are Ar₁ and Ar₂,or the same may be a straight or branched alkyl, alkenyl or alkynylradical, a cyclic hydrocarbon radical or an alkylsubstituted cyclichydrocarbon radical. X₃ and X₄ may also, independently, be alkoxy ordialkylamido radicals, hydrocarbyl radicals and organometalloid radicalsand the like. As indicated supra, Ar₁ and Ar₂ may be linked to eachother. Similarly, either or both of Ar₁ and Ar₂ could be linked toeither X₃ or X₄. Finally, X₃ and X₄ may also be linked to each otherthrough a suitable bridging group.

Illustrative, but not limiting, examples of boron compounds which may beused as an activator component in the preparation of the improvedcatalysts of this invention are trialkyl-substituted ammonium salts suchas triethylammonium tetra(phenyl)boron, tripropylammoniumtetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron,trimethylammonium tetra(p-tolyl)boron, trimethylammoniumtetra(o-tolyl)boron, tributylammonium tetra(pentafluorophenyl)boron,tripropylammonium tetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(m,m-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boronand the like; N,N-dialkyl anilinium salts such as N,N-dimethylaniliniumtetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron,N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron and the like; dialkylammonium salts such as di (isopropyl)ammoniumtetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron,and the like; and triaryl phosphonium salts such as triphenylphosphoniumtetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron,tri(dimethylphenyl)phosphonium tetra(phenyl)boron and the like.

Similar lists of suitable compounds containing other metals andmetalloids which are useful as activator components could be made, butsuch lists are not deemed necessary to a complete disclosure. In thisregard, it should be noted that the foregoing list is not intended to beexhaustive and other boron compounds that would be useful as well asuseful compounds containing other metals or metalloids would be readilyapparent, from the foregoing general equations, to those skilled in theart.

It is important to continued polymerization operations that either themetal cation initially formed from the metallocene, or a decompositionproduct thereof, be a relatively stable catalyst. It is also importantthat the anion of the activator compound be chemically stable and bulky.Further, when the cation of the activator component is a Bronsted acid,it is important that the acidity of the activator compound besufficient, relative to the metallocene, to facilitate the needed protontransfer. Conversely, the basicity of the metal complex must also besufficient to facilitate the needed proton transfer. In general,metallocenes in which the Q ligands can be hydrolyzed by aqueoussolutions can be considered suitable metallocenes for forming thecatalysts described herein, because water (our reference Bronsted acid)is a weaker acid than the ammonium ions used as cation in our preferredion-exchange reagents. This concept allows one of ordinary skill in theart to choose useful metallocene components because stability to wateris a basic chemical property easily determined experimentally or byusing the chemical literature.

In view of the above, when utilizing an activator comprising anon-coordinating compatible anion, the metal component should be onewherein each Q is selected from the group consisting of hydride andsubstituted and unsubstituted hydrocarbyl radicals. Preferred Q ligandsare hydride, C₁-C₁₂ alkyl and C₆-C₁₂ aryl radicals. Most preferred arethose Q ligands selected from methyl and phenyl radicals, particularlymethyl radicals. The preferred metal components species for use with anactivator comprising a non-coordinating compatible anion are those setforth above wherein each Q is methyl or phenyl.

The chemical reactions which occur upon combination of amonocyclopentadienyl metal compound with a non-coordinating compatibleanion activator compound may be represented by reference to the generalformulae set forth herein as follows:

B′ represents a compatible ion corresponding to the general formulae setforth above. When the mono(cyclopentadienyl) metal compound and thenon-coordinating compatible anion activator components used to preparethe improved catalysts of the present invention are combined in asuitable solvent or diluent, all or a part of the cation of theactivator (the acidic proton) combines with one of the substituents onthe metallocene compound. In the case where the metallocene componenthas a formula corresponding to that of the general formula above, aneutral compound is liberated, which neutral compound either remains insolution or is liberated as a gas. In this regard, it should be notedthat if either Q in the metallocene component is a hydride, hydrogen gasmay be liberated. Similarly, if either Q is a methyl radical, methanemay be liberated as a gas. In the cases where the first component has aformula corresponding to those of general formulae of the reactionsequence shown directly above, one of the substituents on the where 2Qis an alkylidine or cyclometallated hydrocarbyl, the substituent isprotonated but no substituent is liberated. In general, the rate offormation of the products in the foregoing reaction equations will varydepending upon the choice of the solvent, the acidity of the [L′-H]⁺selected, the particular L′, the anion, the temperature at which thereaction is completed and the particular cyclopentadienyl derivative ofthe metal selected.

As indicated, the improved catalyst compositions of the presentinvention will, preferably, be prepared in a suitable solvent ordiluent. Suitable solvents or diluents include any of the solvents knownin the prior art to be useful as solvents in the polymerization ofolefins, diolefins and acetylenically unsaturated monomers. Suitablesolvents, then, include, but are not necessarily limited to, straightand branched-chain hydrocarbons such as isobutane, butane, pentane,hexane, heptane, octane and the like; cyclic and alicyclic hydrocarbonssuch as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptaneand the like and aromatic and alkyl-substituted aromatic compounds suchas benzene, toluene, xylene and the like. Suitable solvents also includeliquid olefins which may act as monomers or comonomers includingethylene, propylene, butadiene, cyclopentene, 1-hexane,3-methyl-l-pentene, 4-methyl-1-pentene, 1,4-hexadiene, 1-octene,1-decene and the like. Suitable solvents further include basic solventswhich are not generally useful as polymerization solvents whenconventional Ziegler-Natta type polymerization catalysts are used suchas chlorobenzene.

Catalysts of this invention which are highly productive may be preparedat ratios of mono(cyclopentadienyl) metal compound to non-coordinatingcompatible anion activator of 10:1 to about 1:1, preferably about 3:1 to1:1.

With respect to the combination of a mono(cyclopentadienyl) metalcompound and non-coordinating compatible anion activator compound toform a catalyst of this invention, it should be noted that the twocompounds combined for preparation of the active catalyst must beselected so as to avoid transfer of a fragment of the activator compoundanion, particularly an aryl group, to the mono(cyclopentadienyl) metalcation, thereby forming a catalytically inactive species. When anionsconsisting of hydrocarbyl anions are used, there are several means ofpreventing anion degradation and formation of inactive species. Onemethod is to carry out the protonolysis process in the presence of smallLewis bases such as tetrahydrofuran. Discrete complexes can be isolatedfrom these reactions, but the Lewis base is insufficiently labile to bedisplaced readily by olefin monomers, resulting in, at best, catalystsof very low activity. Another method of avoiding deleterious aniondegradation is by steric hindrance. Anions of the second component whichcontain aryl groups can be made more resistant to degradation byintroducing substituents in the ortho positions of the phenyl rings.While active metallocene polymerization catalysts can be generated bythis method, the complex reaction chemistry often preventscharacterization of the catalytically active species. Steric hindrancecan also result from substitutions on the cyclopentadienyl rings of themono(cyclopentadienyl) metal compound component. Hence, wherein themono(cyclopentadienyl) metal compound used is a [peralkyl-substitutedmono(cyclopentadienyl)] Group IVB metal compound, the high degree ofsubstitution on the cyclopentadienyl ring creates sufficient bulkinessthat the Lewis base generated by the protonolysis reaction not onlycannot coordinate to the metal but also polyarylborate anions withoutsubstituents on the aryl rings do not transfer aryl fragments togenerate catalytically inactive species.

Another means of rendering the anion of the activator compound moreresistant to degradation is afforded by fluoride substitution,especially perfluoro substitution, in the anion thereof. One class ofsuitable non-coordinating anions can be represented by the formula[B(C₆F₅)₃Q′″]⁻ where Q′″ is a monoanionic non-bridging radical asdescribed above. The preferred anion of the activator compound of thisinvention, tetra(pentafluorophenyl)boron, hereafter referred to forconvenience by the notation [B(C₆F₅)₄]⁻, or [B(pfp)₄]⁻, is virtuallyimpervious to degradation and can be used with a much wider range ofmono(cyclopentadienyl) metal cations, including those withoutsubstitution on the cyclopentadienyl rings, than anions comprisinghydrocarbyl radicals. The tetra(pentafluoro)boron anion is illustratedbelow:

Since this anion has little or no ability to coordinate to themono(cyclopentadienyl) metal cation and is not degraded by themono(cyclopentadienyl) metal cation, structures of the ion-paircatalysts using the [B(pfp)₄]⁻ anion depend on steric hindrance ofsubstituents on the cyclopentadienyl rings of mono(cyclopentadienyl)metal compound. the The nature of the cation of the activator component,the Lewis base liberated from the protonolysis reaction, and the ratioat which the mono(cyclopentadienyl) metal and activator component arecombined. Thus, preferred catalyst systems having a non-coordinatingcompatible ion activator are those compounds of the above Formulas I-IV,and, specifically, those species set forth above, in combination with[B(pfp)₄]⁻. If Lewis bases other than that liberated from the protontransfer process are present, they may complex to the metal to formmodified catalysts of this invention.

Catalyst Systems

The catalyst systems employed in the method of the invention comprise acomplex formed upon admixture of the metal component with an activatorcomponent. The catalyst system may be prepared by addition of therequisite metal component and either one or more alumoxane components orone or more non-coordinating anion components, or a combination of both,to an inert solvent in which olefin polymerization can be carried out bya solution, slurry or bulk phase polymerization procedure.

The catalyst system may be conveniently prepared by placing the selectedmetal component and the selected activator component, in any order ofaddition, in an alkane or aromatic hydrocarbon solvent—preferably onewhich is also suitable for service as a polymerization diluent. Wherethe hydrocarbon solvent utilized is also suitable for use as apolymerization diluent, the catalyst system may be prepared in situ inthe polymerization reactor. Alternatively, the catalyst system may beseparately prepared, in concentrated form, and added to thepolymerization diluent in a reactor. Or, if desired, the components ofthe catalyst system may be prepared as separate solutions and added tothe polymerization diluent in a reactor, in appropriate ratios, as issuitable for a continuous liquid phase polymerization reactionprocedure. Alkane and aromatic hydrocarbons suitable as solvents forformation of the catalyst system and also as a polymerization diluentare exemplified by, but are not necessarily limited to, straight andbranched chain hydrocarbons such as isobutane, butane, pentane, hexane,heptane, octane and the like, cyclic and alicyclic hydrocarbons such ascyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and thelike, and aromatic and alkyl-substituted aromatic compounds such asbenzene, toluene, xylene and the like. Suitable solvents also includeliquid olefins which may act as monomers or comonomers includingethylene, propylene, 1-butene, 1-hexene and the like.

In accordance with this invention, when the activator is alumoxane,optimum results are generally obtained wherein the Group IV B metalcompound is present in the polymerization diluent in a concentration offrom about 0.0001 to about 1.0 millimoles/liter of diluent and thealumoxane component is present in an amount to provide a molar aluminumto transition metal ratio of from about 1:1 to about 20,000:1. Where theactivator is one comprising a non-coordinating compatible anion and acation, such activator is present in an amount sufficient to provide amolar ratio of metal component of from 10:1 to about 1:1. Sufficientsolvent should be employed so as to provide adequate heat transfer awayfrom the catalyst components during reaction and to permit good mixing.

The catalyst system ingredients—that is, the Group IV B metal component,the activator, and polymerization diluent—can be added to the reactionvessel rapidly or slowly. The temperature maintained during the contactof the catalyst components can vary widely, such as, for example, from−100° to 300° C. Greater or lesser temperatures can also be employed.Preferably, during formation of the catalyst system, the reaction ismaintained within a temperature of from about 25° to 100° C., mostpreferably about 25°.

Polymerization process

A typical polymerization process of the invention comprises the steps ofcontacting ethylene and a C₃-C₂₀ α-olefin alone, or with otherunsaturated monomers including C₃-C₂₀ α-olefins, C₄-C₂₀ diolefins,and/or acetylenically unsaturated monomers with a catalyst comprising,in a suitable polymerization diluent, a mono(cyclopentadienyl) metalcompound, as described above, and an activator. For example, a catalystcomprising a mono(cyclopentadienyl) metal compound as described aboveand either 1) a non-coordinating compatible anion activator or 2) analumoxane activator. The alumoxane activator is utilized in an amount toprovide a molar aluminum to titanium metal ratio of from about 1:1 toabout 20,000:1 or more. The non-coordinating compatible anion activatoris utilized in an amount to provide a molar ratio ofmonocyclopentadienyl metal compound to non-coordinating anion of 10:1 toabout 1:1. The above reaction is conducted by reacting such monomers inthe presence of such catalyst system at a temperature of from about−100° C. to about 300° C. for a time of from about 1 second to about 10hours to produce a copolymer having a weight average molecular weight offrom about 1,000 or less to about 5,000,000 or more and a molecularweight distribution of from about 1.5 to about 15.0.

In a preferred embodiment of the process of this invention the catalystsystem is utilized in the liquid phase (slurry, solution, suspension orbulk phase or combination thereof), high pressure fluid phase or gasphase polymerization of an olefin monomer. When utilized in a gas phase,slurry phase or suspension phase polymerization, the catalyst systemswill preferably be supported catalyst systems. See, for example, U.S.Pat. No. 5,057,475 which is incorporated herein by reference. Suchcatalyst systems can also include other well known additives such as,for example, scavengers. See, for example, U.S. Pat. No. 5,153,157 whichis incorporated herein by reference. These processes may be employedsingularly or in series. The liquid phase process comprises the steps ofcontacting an ethylene and an α-olefin monomer with the catalyst systemin a suitable polymerization diluent and reacting the monomers in thepresence of the catalyst system for a time and at a temperaturesufficient to produce an ethylene-α-olefin copolymer of high molecularweight.

The monomers for such process comprise ethylene in combination with anα-olefin having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms,most preferably 3 to 8 carbon atoms, for the production of anethylene-α-olefin copolymer. It should be appreciated that theadvantages as observed in an ethylene-α-olefin copolymer produced with acatalyst system of this invention would also be expected to be obtainedin a copolymer of different α-olefins wherein ethylene is not used as amonomer as viewed in comparison to a copolymer of the same or differentα-olefins produced under similar polymerization conditions with acatalyst system which does not use a monocyclopentadienyl Group IV Bmetal compound as defined herein. Accordingly, although this inventionis described with reference to an ethylene-α-olefin copolymer and theadvantages of the defined catalyst system for the production thereof,this invention is not to be understood to be limited to the productionof an ethylene-α-olefin copolymer, but instead the catalyst systemhereof is to be understood to be advantageous in the same respects tothe production of a copolymer composed of two or more C₃ or higherα-olefin monomers. Copolymers of higher α-olefin such as propylene,butene, styrene or higher α-olefins and diolefins can also be prepared.Conditions most preferred for the homo- or copolymerization of ethyleneare those wherein ethylene is submitted to the reaction zone atpressures of from about 0.019 psia to about 50,000 psia and the reactiontemperature is maintained at from about −100° to about 300° C. Where theactivator is an alumoxane, the aluminum to titanium metal molar ratio ispreferably from about 1:1 to 20,000 to 1. A more preferable range wouldbe 1:1 to 2000:1. The reaction time is preferably from about 10 secondsto about 1 hour.

The α-olefin to ethylene molar ratio often bears importantly upon theproduction capacity of a reactor of any design—i.e., whether forsolution or gas phase production, etc.—for production of an ethylenebased copolymer (i.e.—a copolymer the molar ratio of which is 50% orgreater ethylene). The more ethylene input to a reactor in a given unitof time, the greater will be the amount of ethylene based copolymerproduct obtained in that same unit of time. Yet, polymers are designedfor a variety of end services and this design constraint dictates themolar percentage of incorporated α-olefin which must be obtained in thetargeted copolymer product. The “catalyst reactive ratio (r₁)” of acatalyst system defines the property of the system of assimilating anethylene monomer into a polymer molecule chain in preference to aparticular α-olefin comonomer. The larger the r₁ number, the greater thepreference of the catalyst system for incorporating an ethylene monomerrather than a α-olefin monomer. Thus, to achieve a targeted α-olefinmonomer incorporation (C_(α)) in the product polymer, the higher the r₁value of a catalyst system, the larger must be the C_(α)/C₂ molar ratioof monomers used in the reactor, and as the C_(α)/C₂ ratio increases thelower is the production capacity of the reactor.

To achieve a desired level of α-olefin monomer incorporation in acopolymer product, as can be seen, it is often desired to have acatalyst system which can achieve a low molar ratio of C_(α)/C₂, i.e., acatalyst system with a low r₁ is desired. For example, with reference to1-butene, the catalyst systems of this invention wherein the titaniummetal compound has a tetramethyl substitute cyclopentadienyl ligandgenerally exhibit an r₁ value of 6 or less, and typically of 5 or less.Thus, with catalyst systems of this invention an α-olefin incorporationof greater than 20 wt. % can be achieved at a C_(α)/C₂ ratio of 2.0 orless, and typically of about 1.6.

In addition to the benefits of increased reactor productivity which, fora copolymer of a targeted α-olefin incorporation level, which a catalystsystem of lower r₁ values allows, other significant additional benefitsensue from a low r₁ value. Recovery of unreacted monomer, particularlyα-olefin monomer for later reuse adds significantly to production cost.By use of the catalyst systems identified by this invention, the cost ofunreacted α-olefin monomer recovery may be reduced significantly since asmaller quantity of α-olefin monomer can be used to achieve the sametarget level of α-olefin incorporation.

Further, since it is the ratio of C_(α)/C₂ in the medium whereinpolymerization occurs which is critical (i.e., liquid phase, gas phase,or super critical fluid phase, etc.) the low r₁ values for the catalystsystems of this invention permit the catalyst systems to be used in awider variety of polymerization procedures than was heretofore believedto be practically possible. Particularly within this range ofpossibilities is that of the gas phase polymerization of an ethyleneα-olefin copolymer of a greater than heretofore believed possible levelof α-olefin incorporation.

Without limiting in any way the scope of the invention, one means forcarrying out the process of the present invention for production of acopolymer is as follows: in a stirred-tank reactor liquid α-olefinmonomer is introduced, such as 1-butene. The catalyst system isintroduced via nozzles in either the vapor or liquid phase. Feedethylene gas is introduced either into the vapor phase of the reactor,or sparged into the liquid phase as is well known in the art. Thereactor contains a liquid phase composed substantially of liquidα-olefin comonomer, together with dissolved ethylene gas, and a vaporphase containing vapors of all monomers. The reactor temperature andpressure may be controlled via reflux of vaporizing α-olefin monomer(autorefrigeration), as well as by cooling coils, jackets, etc. Thepolymerization rate is controlled by the concentration of catalyst. Theethylene content of the polymer product is determined by the ratio ofethylene to α-olefin comonomer in the reactor, which is controlled bymanipulating the relative feed rates of these components to the reactor.

As before noted, a catalyst system wherein the Group IV B transitionmetal component is titanium has the ability to incorporate high contentsof α-olefin comonomers. Accordingly, the selection of the titanium metalcomponent to have the cyclopentadienyl group to be tetramethylsubstituted and to have an amido group bridged through its nitrogen atomto the cyclopentadienyl ring wherein the nitrogen of the amido group isbonded through a 1° or 2° carbon atom to an aliphatic or alicyclichydrocarbyl group, most preferably an alicyclic hydrocarbyl group isanother parameter which may be utilized as a control over the α-olefincontent of the ethylene-α-olefin copolymer within a reasonable ratio ofethylene to α-olefin comonomer. For reasons already explained, in theproduction of an ethylene-α-olefin copolymer a molar ratio of ethyleneto α-olefin to ethylene of 2.0 or less is preferred, and a ratio of 1.6or less is more preferred.

EXAMPLES

In the examples which illustrate the practice of the invention theanalytical techniques described below were employed for the analysis ofthe resulting polyolefin products. Molecular weight determinations forpolyolefin products were made by Gel Permeation Chromatography (GPC)according to the following technique. Molecular weights and molecularweight distributions were measured using a Waters 150 gel permeationchromatograph equipped with a differential refractive index (DRI)detector and a Chromatix KMX-6 on-line light scattering photometer. Thesystem was used at 135° C. with 1,2,4-trichlorobenzene as the mobilephase. Shodex (Showa Denko America, Inc.) polystyrene gel columns 802,803 and 805 were used. This technique is discussed in “LiquidChromatography of Polymers and Related Materials III”, J. Cazes editor,Marcel Dekker, 1981, p. 207, which is incorporated herein by reference.No corrections for column spreading were employed; however, data ongenerally accepted standards, e.g. National Bureau of StandardsPolyethylene 1484 and anionically produced hydrogenated polyisoprenes(an alternating ethylene-propylene copolymer) demonstrated that suchcorrections on Mw/Mn (=MWD) were less than 0.05 units. Mw/Mn wascalculated from elution times. The numerical analyses were performedusing the commercially available Beckman/CIS customized LALLS softwarein conjunction with the standard Gel Permeation package, run on a HP1000 computer.

The following examples are intended to illustrate specific embodimentsof the invention and are not intended to limit the scope of theinvention.

All procedures were performed under an inert atmosphere of helium ornitrogen. Solvent choices are often optional, for example, in most caseseither pentane or 30-60 petroleum ether can be interchanged. Thelithiated amides were prepared from the corresponding amines and eithern-BuLi or MeLi. Published methods for preparing LiHC₅Me₄ include C. M.Fendrick et a. Organometallics, 3, 819 (1984) and F. H. Köhler and K. H.Doll, Z. Naturforich, 376, 144 (1982). Other lithiated substitutedcyclopentadienyl compounds are typically prepared from the correspondingcyclopentadienyl ligand and n-BuLi or MeLi, or by reaction of MeLi withthe proper fulvene. TiCl₄, ZrCl₄ and HfCl₄ were purchased from eitherAldrich Chemical Company or Cerac. TiCl₄ was typically used in itsetherate form. The etherate, TiCl₄.2Et₂O, can be prepared by gingerlyadding TiCl₄ to diethylether. Amines, silanes, substituted andunsubstituted cyclopentadienyl compounds or precursors, and lithiumreagents were purchased from Aldrich Chemical Company or PetrarchSystems. Methylalumoxane was supplied by either Sherring or Ethyl Corp.

Further, since the full disclosure of U.S. Application Ser. No. 581,841has been incorporated herein, the Examples hereof are identified bydesignations which are consistent with the Example designations of theincorporated application. Examples of the incorporated applicationrelating to the Zr or Hf metal classes of a mono(cyclopentadienyl)transition metal catalyst system are not here repeated (which areExamples A to L) for sake of brevity. Accordingly, not verbatim repeatedherein (but incorporated) are Examples A to L, and certain other doubleletter designated Examples of the incorporated patent. Set forthverbatim herein as repeats of Examples of the incorporated applicationare Examples AT, FT, IT, JT 40-47, 53-56, 58, 67 and 70.

EXAMPLE AT

Compound AT:

Part 1. MePhSiCl₂ (14.9 g, 0.078 mol) was diluted with 250 ml of thf.Me₄HC₅Li (10.0 g, 0.078 mol) was slowly added as a solid. The reactionsolution was allowed to stir overnight. The solvent was removed via avacuum to a cold trap held at −196° C. Petroleum ether was added toprecipitate the LiCl. The mixture was filtered through Celite and thepentane was removed from the filtrate. MePhSi(Me₄C₅H)Cl (20.8 g, 0.075mol) was isolated as a yellow viscous liquid.

Part 2. LiHN-t-Bu (4.28 g, 0.054 mol) was dissolved in ˜100 ml of thf.MePhSi(C₅Me₄H)Cl (15.0 g, 0.054 mol) was added dropwise. The yellowsolution was allowed to stir overnight. The solvent was removed invacuo. Petroleum ether was added to precipitate the LiCl. The mixturewas filtered through Celite, and the filtrate was evaporated.MePhSi(C₅Me₄H)(NH-t-Bu) (16.6 g, 0.053 mol) (was recovered as anextremely viscous liquid.

Part 3. MePhSi)(C₅Me₄H) (NH-t-Bu) (17.2 g, 0.055 mol) was diluted with˜20 ml of ether. n-BuLi (60 ml in hexane, 0.096 mol, 1.6 M) was slowlyadded and the reaction mixture was allowed to stir for ˜3 hours. Thesolvent was removed in vacuo to yield 15.5 g (0.48 mol) of a pale tansolid formulated as Li₂[MePhSi(C₅Me₄) (N-t-Bu)].

Part 4. Li₂[MePhSi(C₅Me₄)(N-t-Bu)] (8.75 g, 0.027 mol) was suspended in˜125 ml of cold ether (−30° C.). TiCl₄.2Et₂O (9.1 g, 0.027 mol) wasslowly added. The reaction was allowed to stir for several hours priorto removing the ether via vacuum. A mixture of toluene anddichloromethane was then added to solubilize the product. The mixturewas filtered through Celite to remove the LiCl. The solvent was largelyremoved via vacuum and petroleum ether was added. The mixture was cooledto maximize product precipitation. The crude product was filtered offand redissolved in toluene. The toluene insolubles were filtered off.The toluene was then reduced in volume and petroleum ether was added.The mixture was cooled to maximize precipitation prior to filtering off3.34 g (7.76 mmol) of the yellow solid MePhSi(C₅Me₄)(N-t-Bu)TiCl₂.

EXAMPLE FT

Compound FT:

Part 1. (C₅Me₄H)SiMe₂Cl was prepared as described in Example BT for thepreparation of compound BT, Part 1.

Part 2. (C₅Me₄H)SiMe₂Cl (5.19 g, 0.029 mol) was slowly added to asolution of LiHNC₆H₁₁ (2.52 g, 0.024 mol) in ˜125 ml of thf. Thesolution was allowed to stir for several hours. The thf was removed viavacuum and petroleum ether was added to precipitate the LiCl which wasfiltered off. The solvent was removed from the filtrate via vacuumyielding 6.3 g (0.023 mol) of the yellow liquid, Me₂Si(C₅Me₄H)(HNC₆H₁₁).

Part 3. Me₂Si(C₅Me₄H) (HNC₆H₁₁) (6.3 g, 0.023 tool) was diluted with−100 ml of ether. MeLi (33 ml, 1.4 M in ether, 0.046 mol) was slowlyadded and the mixture was allowed to stir for 0.5 hours prior tofiltering off the white solid. The solid was washed with ether andvacuum dried. Li[Me₂Si(C₅Me₄)(NC₆H₁₁)] was isolated in a 5.4 g (0.019mol) yield.

Part 4. Li₂[Me₂Si(C₅Me₄)(NC₆H₁₁)] (2.57 g, 8.90 mmol) was suspended in˜50 ml of cold ether. TiCl₄.2Et₂O (3.0 g, 8.9 mmol) was slowly added andthe mixture was allowed to stir overnight. The solvent was removed viavacuum and a mixture of toluene and dichloromethane was added. Themixture was filtered through Celite to remove the LiCl byproduct. Thesolvent was removed from the filtrate and a small portion of toluene wasadded followed by petroleum ether. The mixture was chilled in order tomaximize precipitation. A brown solid was filtered off which wasinitially dissolved in hot toluene, filtered through Celite, and reducedin volume. Petroleum ether was then added. After refrigeration, an olivegreen solid was filtered off. This solid was recrystallized twice fromdichloromethane and petroleum ether to give a final yield of 0.94 g (2.4mmol) of the pale olive green solid, Me₂Si(C₅Me₄) (NC₆H₁₁)TiCl. Me₂ Si(C₅ Me ₄) (NC ₆ H ₁₁)TiCl ₂ .

EXAMPLE IT

Compound IT:

Part 1. (C₅Me₄H)SiMe₂Cl was prepared as described in Example BT for thepreparation of Compound BT, part 1.

Part 2. (C₅Me₄H)SiMe₂Cl (10.0 g, 0.047 mol) was slowly added to asuspension of LiHN-t-Bu (3.68 g, 0.047 mol, ˜100 ml thf). The mixturewas stirred overnight. The thf was then removed via a vacuum to a coldtrap held at −196° C. Petroleum ether was added to precipitate out theLiCl. The mixture was filtered through Celite. The solvent was removedfrom the filtrate. Me₂Si(C₅Me₄H)(NH-t-Bu) (11.14 g, 0.044 mol) wasisolated as a pale yellow liquid.

Part 3. Me₂Si(C₅Me₄H)(NH-t-Bu) (11.14 g, 0.044 mol) was diluted with˜100 ml of ether. MeLi (1.4 M, 64 ml, 0.090 mol) was slowly added. Themixture was allowed to stir for ½ hour after the final addition of MeLi.The ether was reduced in volume prior to filtering off the product. Theproduct, [Me₂Si(C₅Me₄)(N-t-Bu)]Li₂, was washed with several smallportions of ether, then vacuum dried.

Part 4. [Me₂Si(C₅Me₄)(N-t-Bu)Li₂ (6.6 g, 0.025 mol) was suspended incold ether. TiCl₄.2Et₂O (8.4 g, 0.025 mol) was slowly added and theresulting mixture was allowed to stir overnight. The ether was removedvia a vacuum to a cold trap held at −196° C. Methylene chloride wasadded to precipitate out the LiCl. The mixture was filtered throughCelite. The solvent was significantly reduced in volume and petroleumether was added to precipitate out the product. This mixture wasrefrigerated prior to filtration in order to maximize precipitation.Me₂Si(C₅Me₄)(N-t-Bu)TiCl₂ was isolated (2.1 g, 5.7 mmol).

EXAMPLE JT

Compound JT:

Part 1. (C₅Me₄H)SiMe₂Cl was prepared as described in Example BT for thepreparation of Compound Bt, Part 1.

Part 2. (C₅Me₄H)SiMe₂Cl (8.0 g, 0.037 mol) was slowly added to asuspension of LiHNC₁₂H₂₃ (C₁₂H₂₃=cyclododecyl, 7.0 g, 0.037 mol, ˜80 mlthf). The mixture was stirred overnight. The thf was then removed via avacuum to a cold trap held at −196° C. Petroleum ether and toluene wasadded to precipitate out the LiCl. The mixture was filtered throughCelite. The solvent was removed from the filtrate.Me₂Si(C₅Me₄H)(NHC₂H₂₃) (11.8 g, 0.033 mol) was isolated as a pale yellowliquid.

Part 3. Me₂Si(C₅Me₄H)(NHC₁₂H₂₃) (11.9 g, 0.033 mol) was diluted with˜150 ml of ether. MeLi (1.4 M, 47 ml, 0,066 mol) was slowly added. Themixture was allowed to stir for 2 hours after the final addition ofMeLi. The ether was reduced in volume prior to filtering off theproduct. The product, [Me₂Si(C₅Me₄)(NC₁₂H₂₃)]Li₂, was washed withseveral small portions of ether, then vacuum dried to yield 11.1 g(0,030 mol) of product.

Part 4. [Me₂Si(C₅Me₄) (NC₁₂H₂₃)]Li₂ (3.0 g, 0.008 mol) was suspended incold ether. TiCl₄.2Et₂O (2.7 g, 0.008 mol) was slowly added and theresulting mixture was allowed to stir overnight. The ether was removedvia a vacuum to a cold trap held at −196° C. Methylene chloride wasadded to precipitate out the LiCl. The mixture was filtered throughCelite. The solvent was significantly reduced in volume and petroleumether was added to precipitate out the product. This mixture wasrefrigerated prior to filtration in order to maximize precipitation. Thesolid collected was recrystallized from methylene chloride andMe₂Si(C₅Me₄)(NC₁₂H₂₃)TiCl₂ was isolated (1.0 g, 2.1 mmol).

EXAMPLE KT

Compound KT:

Part 1. (C₅Me₄H)SiMe₂Cl was prepared as described in Example A for thepreparation of compound A, Part 1.

Part 2. (C₅Me₄H)SiMe₂Cl (6.0 g, 0.0279 mol) was diluted in 200 ml ofthf. LiHNC₁₂H₂₅ (C₁₂H₂₅=n-dodecyl, 5.33 g, 0.0279 ml) was slowly addedand the mixture was allowed to stir for 3 hours. The thf was removed invacuo and 200 ml ether was added.

To this solution, MeLi (1.4 M, 34 ml, 0.0476 mol) was slowly added. Uponcompletion of the reaction, a small amount of TiCl₄.2Et₂O was added toscavenge the excess MeLi. The solution was then cooled to −30° C. and anadditional 7.75 g (0.030 mol) of TiCl₄.2Et₂O was added. The mixture wasallowed to stir overnight. The solvent was removed and pentane wasadded. The resulting mixture was filtered through Celite to remove theLiCl. The filtrate was reduced in volume and chilled to inducecrystallization of the product. Filtration yielded 4.2 g (0.0087 mol)Me₂Si(C₅Me₄) (NC₁₂H₂₅)TiCl₂.

EXAMPLE LT

Compound LT:

Part 1. (C₅Me₄H)SiMe₂Cl was prepared as described in Example A for thepreparation of compound A, Part 1.

Part 2. (C₅Me₄H)SiMe₂Cl (12.0 g, 0.056 mol) was diluted with 300 ml ofthf. LiHNC₈H₁₅(C₈H₁₅=cyclooctyl, 742 g, 7.42 g, 0.056 mol) was slowlyadded and the mixture was allowed to stir overnight. The reactionproduct, Me₂Si(C₅Me₄H)(HNC₈H₁₅) was not isolated. The thf was removedand 300 ml of diethyl ether was added. MeLi (1.12 M, 1.5 ml, 0.118 mol)was slowly added to form the dilithiated salt,Li₂[Me₂Si(C₅Me₄)(NC₈H₁₅)]. This mixture was cooled to −30° C., andTiCl₄.2Et₂O (19.14 g, 0.057 mol) was slowly added. The resulting mixturewas allowed to stir overnight. The ether was removed in vacuo, andpentane was added to solubilize the product. The mixture was filteredthrough Celite to remove the LiCl. The filtrate was reduced in volumeand chilled to −40° C. to induce crystallization of the product.Filtration yielded 7.9 g (0.019 mol) of Me₂Si(C₅Me₄)(NC₈H₁₅)TiCl₂.

EXAMPLE MT

Compound MT:

Part 1. (C₅Me₄H)SiMe₂Cl (6.0 g, 0.028 mol) was diluted with 150 ml ofthf. LiHNC₈H₁₇ (C₈H₁₇=n-octyl, 3.7 g, 0.030 mol) was slowly added. Themixture was allowed to stir overnight. The reaction product,Me₂Si(C₅Me₄H)(HNC₈H₁₇) was not isolated prior to adding MeLi (2.1 M, 35ml, 0.074 mol) to give Li₂[Me₂Si(C₅Me₄(NC₈H₁₇)]. The solvent was removedvia vacuum and replaced with diethyl ether, then cooled to −30° C.TiCl₄.2Et₂O (8.46 g, 0.025 mol) was slowly added and the mixture wasallowed to stir overnight. The solvent was removed in vacuo andmethylene chloride was used to solubilize the product. The solventmixture was filtered through Celite to remove the LiCl. The filtrate wasevaporated down to dryness and pentane was added. The pentane solublefraction was cooled to −40° C. to induce crystallization of the product.After filtration, Me₂Si(C₅Me₄)(NC₈H₁₇)TiCl₂ was isolated (1.8 g, 0.0042mol).

EXAMPLE NT

Compound NT:

Part 1. (C₅Me₄H)SiMe₂Cl was prepared as described in Example A for thepreparation of compound A, Part 1.

Part 2. (C₅Me₄H)SiMe₂Cl (6.0 g, 0.028 mol) was diluted in 150 ml of thf.LiHNC₆H₁₃ (C₆H₁₃=n-hexyl, 2.99 g, 0.028 mol) was slowly added. Themixture was allowed to stir overnight. The thf was removed via vacuumand replaced with diethyl ether. The reaction productMe₂Si(C₅Me₄H)(HNC₆H₁₃) was not isolated prior to adding MeLi (1.4 M, 45ml, 0.063 mol) to give Li₂ [Me₂Si(C₅Me₄)(NC₆H₁₃)]. The resulting mixturewas then cooled to −30° C. TiCl₄.2Et₂O (8.6 g, 0.025 mol) was slowlyadded and the mixture was allowed to stir overnight. The solvent wasremoved in vacuo and pentane was used to solubilize the product. Thesolvent mixture was filtered through Celite to remove the LiCl. Thefiltrate was reduced in volume and cooled to −40° C. to inducecrystallization of the product. While crystalline material appeared inthe flask at −40° C., upon slight warming, it dissolved back intosolution and therefore could not be isolated by filtration.Me₂Si(C₅Me₄)NC₆H₁₃)TiCl2 was isolated in an oil form by removing thesolvent from the above solution. (4.0 g, 0.010 mol).

EXAMPLE OT

Compound OT:

Part 1. MePhSi(C₅Me₄H) Cl was prepared as described in Example AT forthe preparation of compound AT, Part 1.

Part 2. MePhSi(C₅Me₄H)Cl (6.0 g, 0.022 mol) was diluted with ether.LiHN-s-Bu (1.7 g, 0.022 mol) was slowly added and the mixture wasallowed to stir overnight. The solvent was removed and a mixture oftoluene and petroleum ether was added. This mixture was filtered throughCelite to remove the LiCl. The solvent was removed via vacuum leavingbehind the viscous liquid, MePhSi(C₅Me₄H)(HN-s-Bu). To this liquid whichwas diluted with ether, 28 ml (0.039 ml 1.4 M in ether) MeLi was slowlyadded. After stirring overnight, a small portion of TiCl₄.2Et₂O (totalof 5.86 g, 0.017 mol) was slowly added and the mixture was allowed tostir overnight. The solvent was removed via vacuum, dichloromethane wasadded and the mixture was filtered through Celite. The filtrate wasevaporated down producing a brown solid. Petroleum ether was added andthe mixture was filtered. The brown solid remaining on the filter stickwas discarded and the filtrate was reduced in volume and refrigerated tomaximize precipitation. After filtration and washing with cold aliquotsof petroleum ether, a dark mustard yellow solid was isolated andidentified as MePhSi(C₅Me₄)(N-s-Bu)TiCl₂ (2.1 g, 4.9 mmol).

EXAMPLE PT

Compound PT:

Part 1. MePhSi(C₅Me₄H)Cl was prepared as described in Example AT for thepreparation of compound AT, Part 1.

Part 2. MephSi(C₅Me₄H)Cl (6.0 g, 0.022 mol) was diluted with ether.LiHN-n-Bu (1.7 g, 0.022 mol) was slowly added and the mixture wasallowed to stir overnight. The solvent was removed via vacuum and amixture of toluene and petroleum ether was added. This was filteredthrough Celite to remove the LiCl. The solvent was removed from thefiltrate leaving behind a viscous yellow liquid which was diluted withether. To this, 28 ml of MeLi (1.4 M in ether, 0.038 mol) was added andthe mixture was allowed to stir overnight. A small portion ofTiCl₄.2Et₂O (total of 5.7 g, 0.017 mol) was slowly added. In spite ofthe slow addition, the highly exothermic reaction bumped, thus someproduct loss occurred at this point in the reaction. The remainingmixture was stirred overnight. The solvent was then removed via vacuum.Dichloromethane was added and the mixture was filtered through Celite toremove the LiCl. The solvent was removed and petroleum ether was added.The mixture was refrigerated to maximize precipitation. Filtrationproduced a yellow-brown solid which was recrystallized from petroleumether. The final filtration produced 2.0 g (4.6 mmol) ofMePhSi(Me₄C₅)(N-n-Bu)TiCl₂.

EXAMPLE QT

Compound QT:

Part 1. (C₅Me₄H)SiMe₂Cl was prepared as described in Example A for thepreparation of compound A, Part 1.

Part 2. (C₅Me₄H)SiMe₂Cl (9.0 g, 0.042 mol) was diluted in ether.LiHN-s-Bu (3.31 g, 0.042 mol) was slowly added and the mixture wasallowed to stir overnight. The solvent was removed via vacuum andpetroleum ether was added. This mixture was filtered through Celite toremove the LiCl. The solvent was removed from the filtrate leavingbehind the pale yellow liquid, Me₂Si(C₅Me₄H) (HN-s-Bu) (10.0 g, 0.040mol.

Part 3. Me₂Si(C₅Me₄H) (HN-s-Bu) (10.0 g, 0.040 mol) was diluted withether. MeLi (58 ml, 1.4 M in ether, 0.081 mol) was added and the mixturewas allowed to stir overnight. The solvent was reduced in volume and thewhite solid was filtered off and washed with small portions of ether.Li₂[Me₂Si(C₅Me₄)(N-s-Bu)] (10.1 g, 0.038 mol) was isolated after vacuumdrying.

Part 4. Li₂[Me₂Si(C₅Me₄)(N-s-Bu)] (7.0 g, 0.027 mol) was suspended incold ether. TiCl₄.2Et₂O (8.98 g, 0.027 mol) was slowly added and themixture was allowed to stir overnight. The solvent was removed viavacuum and dichloromethane was added. The mixture was filtered throughCelite to remove the LiCl. The filtrate was reduced in volume andpetroleum ether was added. This mixture was refrigerated to maximizeprecipitation prior to filtering off the olive green solid. The solidwas recrystallized from dichloromethane and petroleum ether yielding 2.4g (6.5 mol) of the yellow solid, Me₂Si(C₅Me₄)(N-s-Bu)TiCl₂.

EXAMPLE RT

Compound RT:

Part 1. (C₅Me₄H)SiMe₂Cl was prepared as described in Example A for thepreparation of compound A, Part 1.

Part 2. (C₅Me₄H)SiMe₂Cl (8.0 g, 0.037 mol) was diluted in ether.LiHN-s-Bu (2.95 g, 0.037 mol) was slowly added and the mixture wasallowed to stir overnight. The solvent was removed via vacuum andpetroleum ether was added. This mixture was filtered through Celite toremove the LiCl. The solvent was removed from the filtrate leavingbehind the yellow liquid, Me₂Si(C₅Me₄H)(HN-n-Bu) (8.6 g, 0.034 mol).

Part 3. Me₂Si(C₅Me₄H)(HN-n-Bu) (8.6 g, 0.034 mol) was diluted withether. MeLi (50 ml, 1.4 M in ether, 0.070 mol) was slowly added and themixture was allowed to stir for two hours. The solvent was removedleaving behind 10.2 g (0.035 mol) of the yellow solid, Li₂[Me₂Si(C₅Me₄)(N-n-Bu)].⅓Et₂O.

Part 4. Li₂[Me₂Si(C₅Me₄)(N-n-Bu)].⅓Et₂O (6.0 g, 0.021 mol) was suspendedin cold ether. TiCl₄.2Et₂O (7.04 g, 0.0212 mol) was slowly added and themixture was allowed to stir overnight. The solvent was removed anddichloromethane was added. The mixture was filtered through Celite toremove the LiCl. The filtrate was reduced in volume and petroleum etherwas added. This mixture was refrigerated to maximize precipitation priorto filtering off a mixture of dark powder and yellow crystals. Thematerial was redissolved in a mixture of dichloromethane and toluene. Asmall portion of petroleum ether was added and the brown precipitate wasfiltered off and discarded. The filtrate was reduced in volume,additional petroleum ether was added and the mixture was placed back inthe refrigerator. Later, 3.64 g of the maize yellow solid,Me₂Si(C₅Me₄)(N-n-Bu)TiCl₂ was filtered off.

EXAMPLE ST

Compound ST:

Part 1. Me₂SiCl₂ (210 ml, 1.25 mol) was diluted with a mixture of etherand thf. LiMeC₅H₄ (25 g, 0.29 mol) was slowly added, and the resultingmixture was allowed to stir for a few hours, after which time thesolvent was removed in vacuo. Pentane was added to precipitate the LiCl,and the mixture was filtered through Celite. The pentane was removedfrom the filtrate leaving behind a pale yellow liquid, Me₂Si(MeC₅H₄)Cl.

Part 2. Me₂Si(MeC₅H₄H)Cl (10.0 g, 0.058 mol) was diluted with a mixtureof ether and thf. To this, LiHNC₁₂H₂₃ (11.0 g, 0.058 mol) was slowlyadded. The mixture was allowed to stir overnight. The solvent wasremoved via vacuum and toluene and pentane were added to precipitate theLiCl. The solvent was removed from the filtrate leaving behind a paleyellow liquid, Me₂Si(MeC₅H₄)(HNC₁₂H₂₃) (18.4 g, 0.058 mol).

Part 3. Me₂Si(MeC₅H₄)(HNC₁₂H₂₃) (18.4 g, 0.058 mol) was diluted inether. MeLi (1.4 M in ether, 82 ml, 0.115 mol) was slowly added. Thereaction was allowed to stir for several hours before reducing themixture in volume and then filtering off the white solid, Li₂[Me₂Si(MeC₅H₃)(NC₁₂H₂₃)] (14.3 g, 0.043 mol).

Part 4. Li₂[Me₂Si(MeC₅H₃)(NC₁₂H₂₃)](7.7 g, 0.023 mol) was suspended incold ether. TiCl₄.2Et₂O (7.8 g, 0.023 mol) was slowly added and themixture was allowed to stir overnight. The solvent was removed viavacuum. Dichloromethane was added and the mixture was filtered throughCelite. The dichloromethane was reduced in volume and petroleum etherwas added to maximize precipitation. This mixture was then refrigeratedfor a short period of time prior to filtering off a yellow/green solididentified as Me₂Si(MeC₅H₃)(NC₁₂H₂₃)TiCl₂ (5.87 g, 0.013 mol).

EXAMPLE TT

Compound TT:

Part 1. Me₂SiCl₂ (7.5 ml, 0.062 mol) was diluted with ˜30 ml of thf. At-BuH₄C₅Li solution (7.29 g, 0,057 mol -100 ml of thf) was slowly added,and the resulting mixture was allowed to stir overnight. The thf wasremoved in vacuo. Pentane was added to precipitate the LiCl, and themixture was filtered through Celite. The pentane was removed from thefiltrate leaving behind a pale yellow liquid, Me₂Si(t-BuC₅H₄)Cl (10.4 g,0.048 mol).

Part 2. Me₂Si(t-BuC₅H₄)Cl (8.0 g, 0.037 mol) was diluted with thf. Tothis, LiHNC₁₂H₂₃ (7.0 g, 0.037 mol) was slowly added. The mixture wasallowed to stir overnight. The solvent was removed via vacuum andtoluene was added to precipitate the LiCl. The toluene was removed fromthe filtrate leaving behind a pale yellow liquid,Me₂Si(t-BuC₅H₄)(HNC₁₂H₂₃) (12.7 g, 0.035 mol).

Part 3. Me₂Si(t-BuC₅H₄)(HNC₁₂H₂₃) (12.7 g, 0.035 mol) was diluted withether. To this, MeLi (1.4 M in ether, 50 ml, 0.070 mol) was slowlyadded. This was allowed to stir for two hours prior to removing thesolvent via vacuum. The product, Li₂[Me₂Si(t-BuC₅H₃)(NC₁₂H₂₃)] (11.1 g,0.030 mol) was isolated.

Part 4. Li₂[Me₂Si(t-BuC₅H₃)(NC₁₂H₂₃)] (10.9 g, 0.029 mol) was suspendedin cold ether. TiCl₄.2Et₂O (9.9 g, 0.029 mol) was slowly added and themixture was allowed to stir overnight. The solvent was removed viavacuum. Dichloromethane was added and the mixture was filtered throughCelite. The solvent was removed and pentane was added. The product iscompletely soluble in pentane. This solution was passed through a columncontaining a top layer of silica and a bottom layer of Celite. Thefiltrate was then evaporated down to an olive green colored solididentified as Me₂Si(t-BuC₅H₃)(NC₁₂H₂₃)TiCl₂ (5.27 g, 0.011 mol).

EXAMPLE UT

Compound UT

Me₂Si(C₅Me₄)(NC₁₂H₂₃)TiMe₂ was prepared by adding a stoichiometricamount of MeLi (1.4 M in ether) to Me₂Si(C₅Me₄)(NC₁₂H₂₃)TiCl₂ (CompoundJT from Example JT) suspended in ether. The white solid recrystallizedfrom toluene and petroleum ether was isolated in a 57% yield.

EXAMPLE 40

Polymerization—Compound AT

The polymerization run was performed in a 1-liter autoclave reactorequipped with a paddle stirrer, an external water jacket for temperaturecontrol, a regulated supply of dry nitrogen, ethylene, propylene,1-butene and hexane, and a septum inlet for introduction of othersolvent or comonomers, transition metal compound and alumoxanesolutions. The reactor was dried and degassed thoroughly prior to use. Atypical run consisted of injecting 400 ml of toluene, 5 ml of 1.0 M MAO,0.206 mg compound AT (0.2 ml of a 10.3 mg in 10 ml of toluene solution)into the reactor. The reactor was then heated to 80° C. and the ethylene(60 psi) was introduced into the system. The polymerization reaction waslimited to 30 minutes. The reaction was ceased by rapidly cooling andventing system. The solvent was evaporated off of the polymer by astream of nitrogen. Polyethylene was recovered (11.8 g, MW=279,700,MWD=2.676).

EXAMPLE 41

Polymerization—Compound AT

Using the same reactor design and general procedure as described inExample 40, 400 ml of toluene, 5.0 ml of 1.0 M MAO, and 0.2 ml of apreactivated compound AT solution (10.3 mg of compound AT dissolved in9.5 ml of toluene and 0.5 ml of 1.0M MAO) were added to the reactor. Thereactor was heated to 80° C., the ethylene was introduced (60 psi), andthe reaction was allowed to run for 30 minutes, followed by rapidlycooling and venting the system. After evaporation of the solvent, 14.5 gof polyethylene was recovered (MW=406,100, MWD=2,486).

EXAMPLE 42

Polymerization—Compound AT

Using the same reactor design and general procedure described in Example40, 300 ml of toluene, 100 ml of 1-hexene, 7.0 ml of 1.0 M MAO, and 1.03mg of compound AT (1.0 ml of 10.3 mg in 10 ml of toluene solution) wereadded to the reactor. The reactor was heated at 80° C., the ethylenewere introduced (65 psi), and the reaction was allowed to run for 10minutes, followed by rapidly cooling and venting the system. Afterevaporation of the toluene, 48.6 g of an ethylene-1-hexene copolymer wasrecovered (MW=98,500, MWD=1.745, 117 SCB/1000 C by ¹³C NMR).

EXAMPLE 43

Polymerization—Compound AT

Using the same reactor design and general procedure described in Example40, 375 ml of toluene, 25 ml of 1-hexene, 7.0 ml of 1.0 M MAO, and 1.03mg of compound AT (1.0 ml of a 10.3 mg in 10 ml of toluene solution)were added to the reactor. The reactor was heated at 80° C., theethylene was introduced (65 psi), and the reaction was allowed to runfor 10 minutes, followed by rapidly cooling and venting the system.After evaporation of the toluene, 29.2 g of an ethylene-1-hexenecopolymer was recovered (MW=129,800, MWD=2.557, 53.0 SCB/1000 C by ¹³CNMR).

EXAMPLE 44

Polymerization—Compound AT

Using the same reactor design and general procedure described in Example40, 375 ml of toluene, 25 ml of 1-hexene, 7.0 ml of 1.0 M MAO, and 1.03mg of compound AT (1.0 ml of 10.3 mg in 10 ml of toluene solution) wereadded to the reactor. The reactor was heated at 50° C., the ethylene wasintroduced (65 psi), and the reaction was allowed to run for 10 minutes,followed by rapidly cooling and venting the system. After evaporation ofthe toluene, 15.0 g of an ethylene-1-hexene copolymer was recovered(MW=310,000, MWD=2.579, 47.2 SCB/1000 C by ¹³C NMR).

EXAMPLE 45

Polymerization—Compound AT

Using the same reactor design and general procedure described in Example40, 300 ml of toluene, 100 ml of propylene, 7.0 ml of 1.0 M MAO, and2.06 mg of compound AT (2.0 ml of a 10.3 mg in 10 ml of toluenesolution) were added to the reactor. The reactor was heated at 80° C.,the ethylene was introduced (65 psi), and the reaction was allowed torun for 10 minutes, followed by rapidly cooling and venting the system.After evaporation of the toluene, 46.0 g of an ethylene-propylenecopolymer was recovered (MW=110,200, MWD=5.489, 20 wt% ethylene by IR).

EXAMPLE 46

Polymerization—Compound AT

Using the same reactor design and general procedure described in Example40, 300 ml of toluene, 100 ml of 1-butene, 7.0 ml of 1.0 M MAO, and 1.03mg of compound AT (1.0 ml of a 10.3 mg in 10 ml of toluene solution)were added to the reactor. The reactor was heated at 80° C., theethylene was introduced (65 psi), and the reaction was allowed to runfor 10 minutes, followed by rapidly cooling and venting the system.After evaporation of the toluene, 35.1 g of an ethylene-1-butenecopolymer was recovered (MW=94,400, MWD=2.405, 165 SCB/1000 C by ¹³CNMR).

EXAMPLE 47

Polymerization—Compound AT

Using the same reactor design and genera procedure described in Example40, 300 ml of toluene, 100 ml of 1-octene, 7.0 ml of 1.0 M MAO, and 1.04mg of compound AT (1.0 ml of a 10.4 mg in 10 ml of toluene solution)were added to the reactor. The reactor was heated at 80° C., theethylene was introduced (65 psi), and the reaction was allowed to runfor 10 minutes, followed by rapidly cooling and venting the system.After evaporation of the toluene, 30.6 g of an ethylene-1-octenecopolymer was recovered (MW=73,100, MWD=2.552, 77.7 SCB/1000 C by ¹³CNMR).

EXAMPLE 53

Polymerization—Compound AT

The polymerization was performed in a stirred 100 ml stainless steelautoclave which was equipped to perform polymerizations at temperaturesup to 300° C. and pressures up to 2500 bar. The reactor was evacuated,purged with nitrogen, purged with ethylene and heated to 200° C.1-hexene (75 ml) was added to the reactor under ethylene pressure. Astock solution of compound AT was prepared by dissolving 6.5 mg ofcompound AT in 12.5 ml of toluene. The test solution was prepared byadding 1.0 ml of the compound AT stock solution to 1.9 ml of 1.0 M MAOsolution, followed by 7.1 ml of toluene. The test solution (0.43 ml) wastransferred by nitrogen pressure into a constant-volume injection tube.The autoclave was pressurized with ethylene to 1748 bar and was stirredat 1800 RPM. The test solution was injected into the autoclave withexcess pressure, at which time a temperature rise of 16° C. wasobserved. The temperature and pressure were reduced continuously for 120seconds, at which time the contents of the autoclave were rapidly ventedinto a receiving vessel. The reactor was washed with xylene to recoverany polymer remaining within. These washings were combined with thepolymer released when the reactor was vented. Precipitation of thepolymer from the mixture by addition of acetone yielded 2.7 g of polymer(MW=64,000, MWD=3.16, 14.7 SCB/1000 C by IR).

EXAMPLE 54

Polymerization—Compound AT

For this Example a stirred 1 L steel autoclave reaction vessel which wasequipped to perform continuous Ziegler polymerization reactions atpressures to 2500 bar and temperatures up to 300° C. was used. Thereaction system was supplied with a thermocouple and pressure transducerto measure temperature and pressure continuously, and with means tosupply continuously purified compressed ethylene and 1-butene (orpropylene). Equipment for continuously introducing a measured flow ofcatalysts solution, and equipment for rapidly venting and quenching thereaction, and of collecting the polymer product were also a part of thereaction system. The polymerization was performed with a molar ratio ofethylene to 1-butene 1-butene to ethylene of 1.6 without the addition ofa solvent. The temperature of the cleaned reactor containing ethyleneand 1-butene was equilibrated at the desired reaction temperature of180° C. The catalyst solution was prepared by mixing 0.888 g of solidcompound AT with 0.67 L of a 30 wt% methylalumoxane solution in 4.3 L oftoluene in an inert atmosphere. This catalyst solution was continuouslyfed by a high pressure pump into the reactor at a rate of 0.56 L/hrwhich resulted in a temperature of 180° C. in the reactor. During thistime, ethylene and 1-butene were pressured into the autoclave at a totalpressure of 1300 bar. The reactor contents were stirred at 1000 RPM. Theyield of polymer products was 3.9 kg/hr of an ethylene-1-butenecopolymer which had a weight average molecular weight of 50,200, amolecular weight distribution of 2.36 and 60.1 SCB/1000 C as measured by¹³C NMR.

EXAMPLE 55

Polymerization—Compound AT

Using the same reactor design as described in Example 54, and using amolar ratio of ethylene to propylene propylene to ethylene of 2.6without the addition of a solvent, the temperature of a cleaned reactorcontaining ethylene and propylene was equilibrated at the desiredreaction temperature of 140° C. The catalyst solution was prepared bymixing 0.779 g of solid compound AT with 0.5 L of a 30 wt%methylalumoxane solution in 24.5 L of toluene in an inert atmosphere.This catalyst solution was continuously fed by a high pressure pump intothe reactor at a rate of 0.9 L/hr which resulted in a temperature of140° C. in the reactor. During this run, ethylene and propylene werepressured into the autoclave at a total pressure of 2200 bar. Thereactor contents were stirred at 1000 RPM. The yield of polymer productwas 2.3 kg/hr of an ethylene-propylene copolymer which had a weightaverage molecular weight of 102,700, a molecular weight distribution of2.208 and density of 0.863 g/cc.

EXAMPLE 56

Polymerization—Compound FT

Using the same reactor design as described in Example 54, and using amolar ratio of ethylene to 1-butene 1-butene to ethylene of 1.6 withoutthe addition of a solvent. The temperature of the cleaned reactorcontaining ethylene and 1-butene was equilibrated at the desiredreaction temperature of 180° C. The catalyst solution was prepared bymixing 0.859 g of solid FT with 30 wt% methylalumoxane solution andtoluene such that the catalyst concentration was 0.162 g/L with an Al/Mmolar ratio of 1200. The preparation was done under an inert atmosphere.This catalyst solution was continuously fed by a high pressure pump intothe reactor at a rate of 1.15 L/hr which resulted in a temperature of180° C. in the reactor. During this run, ethylene and 1-butene waspressured into the autoclave at a total pressure of 1300. The reactorcontents were stirred at 1000 RPM. The yield of polymer product was 3.9kg/hr of an ethylene-1-butene copolymer which had a weight averagemolecular weight of 61,400, a molecular weight distribution of 2.607 and104.8 SCB/1000 C by ¹³C NMR.

EXAMPLE 58

Polymerization—Compound AT

Using the same reactor design as described in Example 54, and using amolar ratio of ethylene to 1-butene 1-butene to ethylene of 1.6 withoutthe addition of a solvent, the temperature of the cleaned reactorcontaining ethylene and 1-butene was equilibrated at the desiredreaction temperature of 170° C. The catalyst solution was prepared bymixing 0.925 g of solid compound AT with 2 L of a 10 wt %methylalumoxane solution in 8 L of toluene in an inert atmosphere. Thiscatalyst solution was continuously fed by a high pressure pump into thereactor at a rate of 0.28 L/hr which resulted in a temperature of 170°C. in the reactor. During this run, ethylene and 1-butene was pressuredinto the autoclave at a total pressure of 1300 bar. The reactor contentswere stirred at 1000 RPM. The yield of polymer product was 3.7 kg/hr ofan ethylene-1-butene copolymer which had a weight average molecularweight of 69,500, a molecular weight distribution of 2.049 and 35.7SCB/1000 C by 13C NRM.

EXAMPLE 67

Polymerization—Compound IT

Using the same reactor design as described in Example 54, and using amolar ratio of ethylene to 1-butene 1-butene to ethylene of 1.6 withoutthe addition of a solvent, the temperature of the cleaned reactorcontaining ethylene and 1-butene was equilibrated at the desiredreaction temperature of 180° C. The catalyst solution was prepared bymixing 1.94 g of solid compound IT with 30 wt % methylalumoxane solutionand toluene such that the catalyst concentration was 0.388 g/L and theAl/M molar ratio was 600. The preparation was done under an inertatmosphere. This catalyst solution was continuously fed by a highpressure pump into the reactor at a rate of 0.42 L/hr which resulted ina temperature of 180° C. in the reactor. During this run, ethylene and1-butene were pressured into the autoclave at a total pressure of 1300bar. The reactor contents were stirred at 1000 RPM. The yield of polymerproduct was 3.9 kg/hr of an ethylene-1-butene copolymer which had aweight average molecular weight of 50,000, 1 molecular weightdistribution of 2.467 and 69 SCB/1000C as measured by ¹H NMR.

EXAMPLE 70

Polymerization—Compound JT

Using the same reactor design as described in Example 54, and using amolar ratio of ethylene to 1-butene 1-butene to ethylene of 1.6 withoutthe addition of a solvent, the temperature of the cleaned reactorcontaining ethylene and 1-butene was equilibrated at the desiredreaction temperature of 180° C. The catalyst solution was prepared bymixing 1.78 g of solid Compound JT with 30 wt % methylalumoxane solutionand toluene such that the catalyst concentration was 0.318 g/L and theAl/M molar ratio was 1400. The preparation was done under an inertatmosphere. This catalyst solution was continuously fed by a highpressure pump into the reactor at a rate of 0.55 L/hr which resulted ina temperature of 180° C. in the reactor. During this run, ethylene and1-butene were prepared into the autoclave at a total pressure of 1300bar. The reactor contents were stirred at 1000 RPM. The yield of polymerproduct was 3.9 kg/hr of an ethylene-1-butene copolymer which had aweight average molecular weight of 72,600, a molecular weightdistribution of 2.385 and 110 SCB/1000 C as measured by ¹H NMR.

EXAMPLES 71-86

Each of the compounds of Examples KT through TT were used to prepare anethylene-1-butene copolymer. The polymerization reactions were carriedout in the same reactor design as described in Example 54. With the soleexception of Example 83, all All polymerizations were carried out usinga molar ratio of 1-butene to ethylene of 1.6 without the addition of asolvent. In Example 83 a 1-butene to ethylene ratio of 2.0 was used. Thetemperature of the cleaned reactor containing ethylene and 1-butene wasequilibrated at the desired reaction temperature of 180° C.

The catalyst solution was prepared by mixing a specified amount of solidtransition metal component with a 30 weight percent methylalumoxanesolution and this catalyst solution was then further diluted in tolueneunder an inert atmosphere. This catalyst solution was continuously fedby a high pressure pump into the reactor at a rate which resulted in thedesired reactor temperature of 180° C., which was the polymerizationtemperature of all examples. The reactor contents were stirred at 1000RPM and a reactor mass flow rate of 40 kg/g was used for all examples.The reactor pressure was maintained at 1300 bar and no hydrogen wassupplied to the reactor. Exact run conditions including catalystpreparation [transition metal component (TMC) and amount (g),methylalumoxane (MAO) volume used (L), total volume of catalyst solution(L) and concentration (g TMC/L) and (g MAO/L)], catalyst feed rate(L/hr), polymer production rate (kg polymer/hr), molar Al/M ratio,productivity (kg polymer/g catalyst) and polymer characteristicsincluding weight average MW (Daltons), molecular weight distribution(MW/MN), melt index g/10 minute at 190° C.), weight percent comonomer(determined by ¹H NMR or ¹³C NMR), and catalyst reactivity ratios (r₁)are collected in Table 1.

By appropriate selection of (1) Group IV B transition metal componentfor use in the catalyst system; (2) the type and amount of alumoxaneneed; (3) the polymerization diluent type and volume; (4) reactiontemperature; and (5) reaction pressure, one can tailor the productpolymer to the weight average molecular weight value desired while stillmaintaining the molecular weight distribution to a value below about4.0.

The above polymerization reactions can be repeated utilizing anon-coordinating compatible anion activator compound in place of thealumoxane so long as the Q ligands are compatible therewith, e.g. Q isnot an alkoxide or halide. More specifically, Q is hydride or ahydrocarbyl radical, preferably a methyl radical. By appropriateselection of (1) Group IV B transition metal component for use in thecatalyst system; (2) the type of non-coordinating anion used; (3) thepolymerization diluent type and volume; (4) reaction temperature; and(5) reaction pressure, one can tailor the product polymer to the weightaverage molecular weight desired while controlling the molecular weightdistribution. The following example illustrates one such polymerization.

EXAMPLE AS

An ionic catalyst was prepared by dissolving 50 ml ofdimethylsilyl(cyclododecylamido)tetramethylcyclopentadienyltitaniumdimethyl and 25 mg N,N-dimethylaniliniumtetrakis(pentafluorophenyl)boron in 10 ml toluene. Dry, oxygen-freehexane (400 ml) was added to a 1 liter stainless steel autoclave whichhad been previously flushed with nitrogen. Under nitrogen, a hexanesolution (2 ml) containing 0.25% triisoprenylaluminum was transferredinto the autoclave by means of a double-ended needle, followed by 4 mlof the catalyst solution. The ratio of titanium containing catalyst toboron containing activator was 3.7. The solution in the autoclave washeated to 80° C. and 4.42 atmospheres of ethylene (0.228 moles) wereintroduced. Polymerization was carried out for 0.1 hours, after whichtime the autoclave was vented and opened. The yield of polyethylene was2.1 grams. This corresponds to productivity of 61 kg polymer/moleactivator atmosphere hour, or 269 kg polymer/mole activator hour.

EXAMPLE AT

An ionic catalyst was prepared and utilized substantially as describedin Example AS except thatdimethylsilyl(N-t-butylamido)tetramethylcyclopentadienyltitaniumdimethyl was substituted for dimethylsilyl(cyclododecylamido)tetramethylcyclopentadienyltitanium dimethyl.

The preferred polymerization diluents for practice of the process of theinvention are aromatic diluents, such as toluene, or alkanes, suchhexane.

From the above examples, particularly as collected in Table 1, itappears that for a catalyst system wherein the Group IV B transitionmetal component is a titanium species of the following structure:

the nature of the R′ group dramatically influence the catalyticproperties of the system. For production of ethylene-α-olefin copolymersof greatest comonomer content, at a selected ethylene to α-olefinmonomer ratio, R′ is preferably a non-aromatic substituent, such as analkyl or cycloalkyl substituent preferably bearing a primary orsecondary carbon atom attached to the nitrogen atom.

Further, from the above data, the nature of the Cp ligand structure of aTi metal component may be seen to influence the properties of thecatalyst system. Those Cp ligands which are not too sterically hinderedand which contain good electron donor groups, for example the Me₄C₅ligand, are preferred.

From the standpoint of having a catalyst system of high productivitywhich is capable of producing an ethylene-α-olefin copolymer of highmolecular weight and high comonomer incorporation, the most preferredtransition metal compound for the catalyst system is of the followingstructure:

wherein R¹ and R² are alkyl radicals having 1 to 6 carbon atoms, each Qis chlorine or methyl, and R′ is an aliphatic or alicyclic hydrocarbylhaving from 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms.

The resins that are prepared in accordance with this invention can beused to make a variety of products including films and fibers.

The invention has been described with reference to its preferredembodiments. Those of ordinary skill in the art may, upon reading thisdisclosure, appreciate changes or modifications which do not depart fromthe scope and spirit of the invention as described above or claimedhereafter.

TABLE 1 Pro- TMC Feed duc- Pro- Catalyst Total TMC MAO Rate tion duc-Produc- Wt Ex. TMC MAO Vol (g/ (g/ (L/ Rate Al/ tivity tivity % # (g)(L) (L) L) L) hr) (kg/hr) M (kg/g) (kg/g) MW MWD MI C4 Method r1 JT 710.540 0.4 10 0.0540 10.4 1.75 5.1 1595 54 0.28 63,600 2.363 11.3 42.01HMMR 4.4 KT 72 2.259 1.8 6 0.3765 78.3 0.51 3.9 1723 20 0.10 84,1004.775 3.3 40.8 1HMMR 4.7 LT 73 1.480 1.2 8 0.1850 39.2 0.46 4.0 1541 480.22 72,700 3.610 7.9 42.0 1HMMR 4.4 MT 74 1.366 1.0 6 0.2277 43.5 0.584.0 1398 31 0.16 78,300 4.601 5.0 40.8 1HMMR 4.7 FT 75 0.859 0.6 5.30.1620 29.5 1.14 4.2 1239 23 0.12 61,400 2.607 13.2 41.9 13CMMR 4.4 NT76 1.441 1.2 8 0.1801 39.2 1.51 4.4 1485 16 0.07 85,400 3.971 3.6 44.01HMMR 4.1 AT 77 0.888 0.7 5 0.1776 35.0 0.56 4.35 1461 44 0.22 50,2002.360 19 24.0 13CMMR 10 OT 78 1.934 1.3 6 0.3223 54.4 0.62 4.3 1252 220.13 64,600 2.494 8.1 43.6 13CMMR 4.1 PT 79 1.900 1.3 6 0.3167 54.4 0.963.75 1274 12 0.07 71,200 2.259 3.8 41.1 13CMMR 4.6 IT 80 0.878 0.8 100.0878 19.6 0.84 4.3 1416 59 0.26 63,600 2.751 6.6 32.4 1HMMR 6.7 QT 810.953 0.9 10 0.0953 23.5 1.32 4.9 1565 39 0.16 64,500 2.342 10 42.81HMMR 4.3 RT 82 0.885 0.9 10 0.0885 23.5 1.68 4.65 1685 31 0.12 71,1002.262 8.8 40.0 1HMMR 4.3 JT 83 1.494 0.5 10 0.1494 13.1 1.02 3.9 721 260.29 78,200 2.617 5.2 40.8 1HMMR 4.6 ST 84 3.053 1.0 12 0.2540 21.8 0.512.9 643 22 0.26 60,500 2.183 8.5 17.62 13CMMR 15.0 TT 85 3.043 1.0 180.1690 14.5 1.11 2.6 708 14 0.16 53,900 2.308 13.8 17.38 13CMMR 15.2 UT86 1.556 1.0 5 0.3132 52.2 0.35 5.0 1258 46 0.27 70,200 2.441 4.6 46.413CMMR 3.7

We claim:
 1. A compound of the formula:

wherein: M is Zr, Hf or Ti; (C₅H_(4-x)R_(x)) is a cyclopentadienyl ringwhich is substituted with from zero to four substituent groups R, “x” is0, 1, 2, 3, or 4 denoting the degree of substitution, and eachsubstituent group R is, independently, a radical selected from a groupconsisting of C₁-C₂₀ hydrocarbyl radicals, substituted C₁-C₂₀hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by ahalogen radical, an amido radical, a phosphido radical, and alkoxyradical, C₁-C₂₀ hydrocarbyl-substituted metalloid radicals wherein themetalloid is selected from Group IV A of the Periodic Table of Elements;halogen radicals, amido radicals, phosphido radicals, alkoxy radicals,alkylborido radicals or any other radical containing Lewis acidic orbasic functionality; or (C₅H_(4-x)R_(x)) is a cyclopentadienyl ring inwhich at least two adjacent R-groups are joined forming a C₄-C₂₀ ring togive a saturated or unsaturated polycyclic cyclopentadienyl ligand; R′is a radical selected from C₁C₃-C₂₀ aliphatic and alicyclic hydrocarbylradicals wherein one or more hydrogen atoms may be replaced by radicalsselected from halogen, amido, phosphido, alkoxy or any other radicalcontaining a Lewis acidic or basic functionality, with the proviso thatR′ is convalently bonded to the nitrogen atom through a 1° or 2° carbonatom; each Q may be independently an univalent anionic ligand, or both Qtogether may be an alkylidene or a cyclometallated hydrocarbyl or anyother divalent anionic chelating ligand with the proviso that where anyQ is a hydrocarbyl such Q is not a substituted or unsubstitutedcyclopentadienyl radical; T is a covalent bridging group containing aGroup IV A or V A element; L is a neutral Lewis base; and “w” is anumber from 0 to
 3. 2. A compound of the formula:

wherein: M represents Ti, Hf or Zr; (C₅H_(4-x)R_(x)) is acyclopentadienyl ring which is substituted with from zero to foursubstituent groups R, “x” is 0, 1, 2, 3, or 4 denoting the degree ofsubstitution, and each substituent group R is, independently, a radicalselected from a group consisting of C₁-C₂₀ hydrocarbyl radicals,substituted C₁-C₂₀ hydrocarbyl radicals wherein one or more hydrogenatoms is replaced by a halogen radical, an amido radical, a phosphidoradical, and alkoxy radical, C₁-C₂₀ hydrocarbyl-substituted metalloidradicals wherein the metalloid is selected from Group IV A of thePeriodic Table of Elements; halogen radicals, amido radicals, phosphidoradicals, alkoxy radicals, alkylborido radicals or any other radicalcontaining Lewis acidic or basic functionality; or (C₅H_(4-x)R_(x)) is acyclopentadienyl ring in which at least two adjacent R-groups are joinedforming a C₄-C₂₀ ring to give a saturated or unsaturated polycycliccyclopentadienyl ligand; each of R¹ and R² are independently selectedfrom C₁-C₂₀ hydrocarboyl radicals; each Q is independently selected fromhalide, hydride, substituted or unsubstituted C₁-C₂₀ hydrocarbylradical, alkoxide, aryloxide, amide and phosphide radicals with theproviso that Q is not a substituted or unsubstituted cyclopentadienylradical; R′ is selected from C₁C₃ -C₂₀ aliphatic and alicyclichydrocarbyl radicals with the proviso that R′ is covalently bonded tothe nitrogen atom through a 1° or 2° carbon atom; L is a neutral Lewisbase; and “w” is a number from 0 to
 3. 3. The compound of claim 2wherein M is Ti.
 4. The compound of claim 2 where: M is Ti; and R¹ andR² are each independently selected from alkyl and aryl radicals havingfrom 1 to 20 carbon atoms.
 5. The compound of claim 2 wherein R′ isalicyclic.
 6. A compound of the formula:

M is Zr, Hr or Ti in its highest formal oxidation state (+4, d^(o)complex); (C₅H_(4-x)R_(x)) is a cyclopentadienyl ring which issubstituted with from zero to four substituent groups R, “x” is 0, 1, 2,3, or 4 denoting the degree of substitution, and each substituent groupR is, independently, a radical selected from a group consisting ofC₁-C₂₀ hydrocarbyl radicals, substituted C₁-C₂₀ hydrocarbyl radicalswherein one or more hydrogen atoms is replaced by a halogen radical, anamido radical, a phosphido radical, and alkoxy radical, C₁-C₂₀hydrocarbyl-substituted metalloid radicals wherein the metalloid isselected from Group IV of the Periodic Table of Elements; halogenradicals, amido radicals, phosphido radicals; alkoxy radicals,alkylborido radicals or any other radical containing Lewis acidic orbasic functionality; or (C₅H_(4-x)R_(x)) is a cyclopentadienyl ring inwhich at least two adjacent R-groups are joined forming a C₄-C₂₀ ring togive a saturated or unsaturated polycyclic cyclopentadienyl ligand; R′is a radical selected from C₁C₃-C₂₀ aliphatic and alicyclic hydrocarbylradicals wherein one or more hydrogen atoms may be replaced by radicalsselected from halogen, amido phosphido, alkoxy or any other radicalcontaining a Lewis acidic or basic functionality, with the proviso thatR′ is covalently bonded to the nitrogen atom through a 1° or 2° carbonatom; each Q may be independently an univalent anionic ligand selectedfrom a halide, hydride, or substituted or unsubstituted C₁-C₂₀hydrocarbyl, alkoxide, aryloxide, amide, phosphide, or both Q togethermay be an alkylidene or a cyclometallated hydrocarbyl or any otherdivalent anionic chelating ligand with the proviso that where any Q is ahydrocarbyl such Q is not a substituted or unsubstitutedcyclopentadienyl radical,; “w” is a number from 0 to 3; T is selectedfrom radicals of the formula (CR³R⁴) wherein R³ and R⁴ are independentlyselected from hydrogen and C₁-C₂₀ hydrocarbyl radicals; and y is 1 or 2.7. The compound of claim 6 wherein M is Ti.
 8. The compound of claim 6wherein: M is Ti and R³ and R⁴ are selected from hydrogen, C₁-C₆ alkylradicals and C₆-C₁₂ aryl radicals.
 9. A compound of the formula:

wherein R¹ and R² are each independently a hydrocarbyl radical, each Qand Q′ is independently a halide or a C₁-C₂₀ hydrocarbyl radical, R′ isan aliphatic or alicyclic hydrocarbyl radical having from 1 3to 20carbon atoms and R′ is covalently bonded to the nitrogen atom through a1° or 2° carbon atom, L is a neutral Lewis base where “w” denotes anumber from 0 to 3 and each R is, independently a C₁-C₄ hydrocarbylradical or hydrogen, x is 0, 1, 2, 3 or 4, or two adjacent R groups mayjoin to form a C₄-C₁₀ ring.
 10. The compound of claim 9, having theformula:

wherein R¹ and R² are each independently a hydrocarbyl radical, each Qand Q′ is independently a halide or alkyl radical, R′ is an aliphatic oralicyclic hydrocarbyl radical of from 1 3to 20 carbon atoms and R′ iscovalently bonded to the nitrogen atom through a 1° or 2° carbon atom,and L is a neutral Lewis base where “w” denotes a number from 0 to 3.